Nitro Grouporg.synt

7/23/2019 Nitro Grouporg.synt

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THE NITRO GROUP INORGANIC SYNTHESIS__ _______________________ ____ !_____ "_+________ 8 _77_ 9___.:+%;(-!_$ 7.)___&_1__6_____$_%

3____%_;4________


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_______ ________ ________________ _ ____#________&_5______ ___#________ _________ ___ ______________ ___#_______ ______________ _________ ________36$____ '_____.__7 ___.7++61_+)_8)+)916_3++___/8)+)916_31_%_:___;#%&:&%


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5.7 E * *?D* / 149< Con.ersion o' Nitro Co2o0n%s into Other Co2o0n%s /;=6.1 B* (?, G, * *? ) / 159"4_4__ ;__$_8_________3&_%_# _$___&$__,__&_%___(_ _ _2"4_4__ __%$__.__9____%_ _ _"_"4_4!_ 7_%_&__.__9____%__ _ _"_"4_4__ =___&__ __.________0______$_'________ $_______ _8___%__ _ _"

6.2 ? * ? / 1676.3 B / 170"4!4__ 3______


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.$______0__&____$________$_____$%___%______8___$_&___0_______&_8___%____________________0&_8___8___&____4_________________0_________________.__6_____0___%__0___$__&_______&__8________________$%_________ ___ __&__%___ ____&___$____ ___$__%_ &_$_____ _0_ &_8___%__ __&__ $__ _____$8____1_____$___1________1_$_%___________%__4____________%_%___$______&___________1_6___$___$&__.____.____$_______

.$______ 0$&____ _0_ ____ 0___%1_ 6______._%__$_&__&__________$_____ _0_ __&____$%.$_&___ __$___$._____$__%_$____$___$_&___________&__8__________$_&_4______


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3_ $___2____ 2____$__&_&__G!4!4_F___$_____3, _1______$___$______1__%_______%_________________/ _1________$_______& __________&$____________ _______ _____

__/_ ____________8_ ______

3_ &___&_$88____8_____$__;3_ &_______8_____$88____8____8_%__ _______&$______

=__ _1_%_$$__&_&__G_4!4_F_______=_- _1_%_$$__&___G4_4_F__%_&____= %_&_&______&$___%__8_%_==O _1!_%_&______1"_%_&_$____1______@______=+3= %______$_%_&$_____$__=93, ___1__%_8_____$8______%___=9+ %_8________$__=9< _1__%_8_____0__8$8_%_=9_ _1!_%_8_________8%$________=9__ %_8_________0__%_%_$ %_______%___$&_____%4_4 %_$______8___&__&___%4_4 %_$__________&__.___%_ _1_____#%_____________(___$__% _1!____#%_____________(__$__%_ _1_____#%_____________(___$__%0 _1_____#%_____________(0____&___=3_ _ _1__%_$$__&_&__G_4_4_F_&_$__+ ___&________+_ ______4_4 __$____8___&__&____9=_ __$8_____%____$$___8 ___8_%$____/=3 ______8_%________$8_%_

/_____&__%_ ______8_____________________%__%_9 ,_3 "_&____________&_$&_%.9_ 8_____9+9 __8__________8_____9_9 8_____8________ _____8___&&___8_%__9_ __8_____8_____________%___ __&________, ___%____8_&_____&___8$__ ,___ ___$____,9_ __8__________,__ ____________;_=9_ __________%_8__________

;95 ____$8______$__%___;_3< ____$_____$88____8_0_____%_;


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;_ ___________0____1_______+; _________&_______$__0_____$&____.i ABBREVIATIONS

1INTRODUCTION___________ ___________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________ ________________________________________ ______ __________________________________________________________________________________________________________________________________ ____________________________________________________________

__________ ___ ________ ___ _____ _________ ____ ___________ __ !_______ "_"_ ___ "_#_$____________________________ _____________%__________________________________________________ ____%_______________________ __________ _____________________ ____________________ _________________________________%______________________________________ ___ _______ ________ ___ _____ __________ ____ _______________ _________ _________ ______________________________&______________'____________________________________________________________________________(_____________________)______________________________________________ ___________________________________________________%_________/R NO2Ar NO2ArNH2R CH NOHR XR CHO R

NO2CH3NO2RN3X = Br, I, OTsArHRHRNH2S)hee // Preparation of nitro compounds__ _______________________ ____ !_____ "_+________ 8 _77_ 9___.:+%;(-!_$ 7.)6>=">4-_5_ !__ ________8__.__+_____)_____________._________________"_&">4>'_3_ ______9________1_______________755_&">77'_;_ 1________$__9__


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Ar NO2R Nu,*?DR HR NH2Ar NH2F*? *? *-*??*RCNORCO2HRCHOS)hee /1 Reaction of nitro compounds

1 INTRODUCTION

2PREPARATION OF NITROCOMPOUNDS1/ NITRATION O# HYDROCARBONS1// Aro(ti) Co2o0n%s________ _______ __ _ _______ ________ ________ ________ ___

____ ________ ___________ _________ ____ __ _________ __ ___ __ ___ __________

___ ___ __________ __ _____ ____________ __ _____ _______________ _________ __ ________ __________ _______

__ ______________________ __ ________ _________ __ _______ __ __ ___ _________ _______ ______

____________ ___ _______ _______ ______ _____ ________ ___ ___ __ _ ______ __ _____ ____

__ ___ _________ __ _____ _____ ____ __ __________ _______ ____________ ____ _______ __

___ _ ___ _ __________ ________ ___ ______ _________ ________________ ________

______ _____ !"_# _____ __ ____ _________ __ _____ ______ _______ __________ __

_______ ___ _______ _______ ______ ____ ___ ____________ _____ __ _ _____ ___ ___ __

_______ _______ ____ __ ________ ____ ________ !__________ ___ ___________ _ ___

____ __ "___ _ _____ ___ ______ _______ _____ ___ _________$_ _#%!"& ' ____ _______

%_(")_ %_")_ _____________ _____ %+")_ %,_ -,&_ +%&("&%_ +,&("&%_ ,("&%_!____.

%#/ _# 0"!"_ ' ____ _______ %_(")_ _+&_ (+)_ -,/ _# 0+"_!"_/ _#!"_+ ' ____

_______ _+&_ __+)#/ _# !_"1 __ !_") ' ____ _______ %_(")_ %!"&_ _+&__ __#/ _#

!"_+-,)


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_ !"_+,2/ __ _# _.____________ _____ _ __ _______ ________ ____ __ __________ _______ ___ ___ ___

_____ __ _____ _________ +___ ___ ______ ___ ____ ________ ________ _

__________ _______ __ __3______

________ ________ ___ ________ ________ ____ ____ _____________ ______ ________________& _ __________ ______ _______ _______ ________ ____ _______________

_______ ____# __ ________ __ ______ _____ __ _____3_ ______ ___ ___

__ ____ ____ ________ __________ __________ _______ __ ___ ____ __ ______ __ _______ __

___ _______ __ ___ __________ ____ ___ ____ _____ ______ ___ ___________& ___ ___ __

!____.% __ ______________ ____ _____ _______ ___ _________ _____ __ ___ _______ ________

_______ __ ______ _______ ________________) _ __ ____ __ ____ ____ _______ ________

_ ____ _______.____!____ ____ ________ _____ _ ______ _____ _______ ___ ___ ________

__ ___.________3__ _ 4_5 _________1 +_____ ______ _________ _ ___________ 6._7

_______ ______ ___ _______ __ ______ ________ __ _______ ____ ____ ___________2

!_________ __3___.3__ _______________________ ____ !_____ "_+________ 8 _77_ 9___.:+%;(-!_$ 7.)


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____ _ _______ ___._____________ ___ __ __ ___ __ __._________ ___ _______ __ ______

__ ___ _______ __ __ _________ __ _____ __________ __ ____________ _______ _____ __

______ _________ ___ _______ __________%_______ ____ _______ __ __ _________ ___ ___ ________

_________ ____ __ _.__________ ;

____ ______ ______ ;:# __ 3_______ ;:# ________ ___ ______ ________ _7 __5# ___ __________ __ ___ ________ __________ ___ ________ ___ ______

_______ ____ ___ ____________ __ ______ =___ __& __ __)#_______ ___ _____ __________ __ ______ ______ _ _ ___._____ ______

_____._____# ____ _______ __ %+ __ _ ________ _____ __ @_ !"&__& :______

_______ _______ ____ _______ _ ___ _______ __ &.___________ _____ __ ____ ______________ ___

&.___________ 1.___________)H3C HNO3, Ac2O H3C H3C H3CF HNO3, Ac2O F FF

NO2NO2NO2NO2NO2NO2+ +6%Zeolite-,20 P, 30 0% 94%+ +Zeolite-,0J20 P, 30 18% 3% 79%

___#___#H3CHNO3Yb(OTf)3H3CH3C H3CH3C HNO3NO2H3C H3CNO2NO2NO2NO2NO2O2NNO2Zr(OTf)465%+

35%+ +ClCH2CH2Cl52% 7% 41%reflux____)#9 PREPARATION OF NITRO COMPOUNDS:______ ____________ __ _ ____ __ ____ ______ ____ __ __ ____

__ ______ _ ____ __


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___________ ________ ________ _ _____________ __ ____ _________________ __ 5

_____ __ _______ ________ =__ __1#__2_ ____ ___ ______ ___ ___ ______ _______ __ _________ ___ ___

________ ____ _________ ______ __ ______ _______ __ __ ____________ ___ ____ ________

__ _________.

___ ______ ____ ________ ________ ___ __ ________ _ ___________ __ ___ _.____._________ ___ _______ _


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C2H5C2H5NO2C2H5NO2NO2N2O5, HNO3N2O5, HNO35 P, 5 25 P, 10 __


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_-_!# __ ______________ ________ _,__# _____ _________ ___ &.____ ____________ ;_ __

N NNO2N2O5MeNO2,NaHCO368%

__#OONO2-O3OONO2ONO2-O3ONO2o-52%, m-48%J10 PMeMeCH2Cl2, 0C58% (o:m:p = 22:19:59)___7#____#ONO2-O3ONO2____#< PREPARATION OF NITRO COMPOUNDS_________ ____ ___ _______ _______ _ ____ ____ __ ___ ______ _______

________ ____ ___ ________ ____________ __ ___ _-_!O_,__ ______ =__ _____4 ___

_____ ________ ______.__ _________ ________ __ ___ __ ____ _______ ____ ___ ____

__ _________ ___. __________ ______ ________ _ ____ _______ ;_ __ __ ______3__ ____ !"_ __ _ ____ ________

______ _____ ____ _ ___________ __________ ___________ ________ __________ ________

___________ ______ ________ ____ ___________ ____ ___ ___ ____________&70______ _______ __ ____________ __ E_______ ____ !_") ___ ___ ________

___ _____________ __ ______ ____ __ ____ ________ =___ ___) __

___1#_&_ ___ _______ __ ____ _______ ______ _ ___ _______ ________ __ ___________# __ ___

_________ __ ___________,__ _______ &.____________ __ __ _______ _


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; _______ __ ___ _______ __ ________ ____________ _________ ________ ___________ ___ ____

______ ________ _______ _____ ____ ______ _________ ___ ______ _____________

______ _______ __ ___ +.+ ___ __ ____ _ ______ ___ __________ ________ __ ______________ ___ _______ _ ___ ___ _____ ___ ___ ____ _ _______

____ ___ _)7__ ________ ___________ __________ _.___________ _.___________ _._________ ___._.

__________ _______ ____ ______ __ ________ ___ ___ __________ __ _________ _ ________

__ __ __ ________ ___ ___ _________ __________ ____________ =__________ _______ _______ __ _ ____ ________ _______ ___ ________ _______ ___ __

___ ____ ________ __ ___________ "__ ___ ________ _______ __ ________ ____ _______ ____

_ _______ ______ ________ ____________ ___ ___ ____ __ _.____________ __ __ _75_&_ (___

____ ___ __________ _______ __ ________ ____ ___ ______ __ ___ ____ ___ ___

________ __ 27


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(________ 0_____ +______ ______ G___ 5#_ 0___

%!"&_ ___"_6._7++)

_____

_.&__.__.2_'_

___________ __ _________ __ _________17___ ________ _______ ___ ___ __________ __ _________ ___ ________

_ +_______:____ 2 _ "_____ (________ ____ &.____________ _____ __ _ ____ ________ ______

___ ______ _________ __ ________ __ ___ _______ __ _____ ___________ !_") _ ___

_______ __ ______ _____ __ ______ __ ___ _________ ________ __________ _______ =__

___2#_1_ ___ _______ __ _____ ____ ______ ______ _ ___ _______ __ _____ _____ _ _______

__ _____ ____ _______ __ ______ _________ _____ ___ __________ ____________ _____

_._____________ __ ________ _ 2&2)5 ____ __ ___ _______ ___________ __ !_") _

___ _______ __ "_ ____ ___#_1_OOHH HOOOHH HO


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NO2CH2Cl21 , 25 PHNO3, Ac2O___1#2) AcONa HO2N H

CO2Me1) N2O4, I2CH2=CHCO2Me___2#CO2RONO2CO2RNO2OMe1) t-BuLi,J78 P71%2)R=___)#2.1 NITRATION OF HYDROCARBONS//

__________ ____________________________________________+____ _____ 0_____ ______ G___ 5# 0___

!"__"&

42 1&

!"%.3_____


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_# 6!"__ _4.____.2_ ;__ _%,

_# _______

7 2)

!_!"_+_ !%)#&!"

__"%

2 12

!_!"__ !_!"&_____ ________

)_ 1

!_!"__ ;_%"+%_+%_"%


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_______ _________ __ __________ ____ ______ _____ _ ____ ____ _________ _____ __

_______ _______ _________ __ ______ __________ __ ___ __________ ___________ _______

____ _______ ______ _____ __ _______ =__ ___


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H-zeolite___


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66%1) PhSeBr2) AgNO2/ HgCl23) H2O21) PhSeBr__&__&)#

MeO OMeOMeCH3MeO OMeOMeCH3NO21) AgNO2, I280%2) Et3N__&_#NH4NO3, TFANO2

70%HBF4, CH2Cl220 P, 15 __&1#/9 PREPARATION OF NITRO COMPOUNDS__ __ _________ _ ____ ____ ___ ________3__ _____________


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__________ %_______ ____ _______ __ __ _____ _____ _______ ___ ______ __ ________ __

____ ________ _________ ___ _________ __ _____ __ ___ _____ _ ______________.________

_______ ____ _____ ________ __ _ __________ ______ __ ______ _________ ______

______ 177 __O___#____ _ _______ %.__ _ _________ @_-,) __

_________# _____ _ ________ !"_-,)_ _____ __________ _______ __________ __ ___ _______ ______ _______ __ _____

____________ ______________ .____ _______ _____ ___________ __ _______________


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___ __ ______ ____ _______ ________________4_ ________ _ ______ ___ ___ __________ __

_____ .____ _______ _____________ ______ ________ ____ ______________ __________

_______ ______ __ _ ___ __ _________ _______ ______ ___ __ ________=__ __)_#_4&

+____ __ ______ ___ __ ______ __ __ _______ ____ _______________ __

____ .__________ _ 2)25____ =___ __)_ __ __)_4) ___ ________ ______

___ ______ ___________ ___ ___ __ _____ __ ________________ _ ____ ________

______ __ ___ _______ ___________ __ ___ __ _____ ____ !"_ ____ __ .____ _______ _______________

__ _ _____ ______/ __ __ __________ _______ __ ______ _________41_ ___ __.___ ________ __ .____ ______ ____ _____ ___ ___ ________

_ ____________ ___________ ______.________ ________ __ _ ___________ ______.N("

______ ______=__ __))#_42OSiMe3

C(NO2)4DMSOONO290%__)OSiMe3RXC(NO2)4DMSOOXR

NO2X = H, OMe; R = H, Me92J95%__)_#OAc(CF3CO)2OOO2NHNH4NO3100%__)_#OAcRHNO3-Ac2O

ONO2R75J92%15J22 P__)7#/< PREPARATION OF NITRO COMPOUNDS

.!____ _______ _____ ___ ________ ____________ ___ ______ _________ ___ __________


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________ ______ __ ________ __ _.__________ ___ (_____ &_______ _______ __ _________

___ (_____ 1__#_ (________________ __ _____ .____ ______ ___ ___ __ _______3__ _

_____ ________4


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OHMe NO2Me NO2NaBH465%Ac2OAl2O3

60%DMAP__)1#Me3SiONO2ONO2CrO3DMSO73B*C Q? (%)__))# 612.1 NITRATION OF HYDROCARBONS/

_____ ___ _______ __ ___ ______ __ .___ ______ ____ ______ ______ _________ ____

_____ ________ ______ ___ _________ __ .____ _______ %_______ ____

____________ ___________ _ ____ __ ____ __ ____ ____ ___________ _ ________

____ ______ _______& ____ __ ___ __ ___ ______ _______ __ ___ ____ ____________ _____ ________

_ _______ _______ __________ ______ __ ____ ___ _____3__ ________ ___ (_____ 2___ _____

_________ ___ !__ _______#_; _ ______ ____ ___ _______ __ __3_ _______ ____ ______ ______ __

_1 M+ _____ __3___ _______________ __ ___ _____2 M+# =__ __)4#_ &(_____ ________ _______ ___ ___ _______ __ ___ ______ ____ ___

_________ ,__ __________ ___ __ 6!"_ _ ___ _______ __ _4.____.2) __ ______ __

______ __ ____________________ _______ ________ ____ ________ ;0_ 77# ________ _______ __ ____ ___.

_____ =__ __)#_1_____ __ _________ ____ ________ _. _.________#.__&._______ ____ ___

____________._____ ________ __ _______ __________ =__ __17#_2 ____ ____ ____

;0_.77.!"_ __ _______ ____ ____________ __________ __ _________ ____ ___ ______ ___ ___ ____

_________ ___ _______________ ;__________ ______________ ________ _____ ____ ____.__________

_________ __________ ____ ___ "_____ _____ _____ _______________ ___ ________ __ ____

___________ ___ ___ __ ___ _______ __ ___ ___________ _______ ____ _____

______ =__ __1_#_ ____________ __ _______ ________ __ _ _________ ________ ____

_______ ________ ___________ ____ __________ __ _____ _________4___4______________ _____3__ ___

____.___ __ ___ ________ ____ ______ _______ ; ______._____ _$_# __

&7 M+_ ___ _______ __ _.____________ ___ _________72 +__________ ___ _______ _____ __ >0."!"$ >0!"_

______ ____ 7_17$___ 7__2$__ _____ _ __________ __ ______ ___ __ ____________ _______ _________ __;0_.77.______ ____ ________ _ __ ______ ___ ________ _______ __

___ _______11 SYNTHESIS O# NITRO COM!O"NDS BY OIDATION11/ Oi%(tion o' Aines

___ ______ ________ __ _______ _____ ___ ___ ___________ _______________ __ ____ ________ ________ __ ________ __________ _______ __ ________ ____

_________ _____ ____________ __ ________ __ _______3_ __ ______ _______ ________

=_______ ________ _______ ___ ___ ________ __ _______ _____ ___ ___ ____ ________ ____________ _ ____ _______(________ _______ _____ ______ ________ ________ __ _3__ __ ____

___ ____________________ __________ __ ______ _____ ________ _______ _ ___ _______

__________7508_$%_,______@_ ______ ____________ ____""____________________________________________7____-:___'_$%'_,8_>_________ ________ _____ __ ___#___ ____________ ______ _ ___ ____ ____ ___ _____________ ____________ _________(__________ __ ________ ____________

_____________________ _______7-:__'__8_________________ "_________________________________#_______ ____________________0__#__"__________#___________ _ ___ ______ _______ ________#_"_ ___ _____

___#___#_______ __________@__ _____ ______""_________________" __________________ _______ ________"__

_________ __ ___ _7-:__'_.8_._________________ _____"___________@_7-:__'_)8_)________________________________ ________ "____________""________________#_________________ _________

____ "_________ __________ ___________ _______ ___________________ __ "____________

_______________________________(___________'____!__#______________________________ ____ ______ __ __ ______________________ ___ _#__________________ __ ____ ________# _______!________________"_ _______ __ "_ ____ ____ ____ _ __ ___ ___ __ ____ ___ _________ ___ _________

_"____ _______"__________________ ________________ ___C6H13CHOCH3CN

OHC6H13C6H13NO2OHCF3CH3NO2BI, 24 DBU(0.1 SA)BI, 24 65%DBU(1 SA)CH3CH2NO2

95%+ C6H13CH2NO2OHCF3OH+7'_'87'_,8HOOH


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NO2OHEt3N 0.5 h4 h95902:1

Ph O**?2:1cat.N

Q? (%) syn:anti3

I+ O2NCH2CH2OH7'__8CHOKF, i-PrOH OHNO2NO2

OO OOOHCH3CHOBI, 6 90%Bu4NF3H2O (0.48 SA)0J6 P, 23 +CH3NO2O2N52% (anti/syn = 62/38)7'_.87'_)8HOOHNO2CH3NO294%0 P, 30 TMG(0.1 SA)+7'_$831 THE NITRO-ALDOL (HENRY) REACTION

________ __ _______________________________________________0___ __ __ __ 2___ ___

_ __ __ 2 ____ _ _ ___N____7;8_

_7__O___8 &_"_0_1__

_-_1_______ '.2_'01$


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2_'01$ _2_1 _+__'_______2_, __2_'2_$01$ _2_1 2_E2__

_0_1____$1__$__)_ $)

2_'2_$2_1 2_E2___0_1____$1__'____ $)_172_$8.2_$01$ 2_'2_1 E$___$__) $_E$__

_______ $_E_$1' ._ $$2_'2_$01$$,__


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OHCH3NO2

CHOCH3CH3CHOCH3

CH3OHCH3CH3CH3NO2

O CHOOOHCH3NO2OHCH3NO2OHCH3CH3OH

PhNO2NO2CH3CF3OH

CF3CHOHOHOHPhNO2OEtOEtNO2CH3CF2HOH

CF3CH

OEtOHOOCO2HNO2OHCl NNO2OHOHHONO2OHOH

OHOHPhNO2

3.1 PREPARATION OF-NITRO ALCOHOLS330___ ________ ____ _________ _____ ______________ ___ ____ ___ ______________ __ " ___ ________________ _________________________________ _#________ ____ _

________________________________ "__


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____________ ____ "_5_,0@ '__$1____%)__2______@__5_______________ _____ __ ______________ ___________#_________ _______________ _____________ ______-:__'________________________________

_ ______ _____ ___#_____ ____ _ ______________ __ "________________________________________ "

____ ____________" ____ _________________$__:____ "___________________@O_+E____

%__2__________________________ _#________ ____ _ __________#_________

_____________"________"_____ _ ____ _7-:__'__8______________________________________ ________ _____ __ ______________ _

___ __________ "__________ ______________ "_____ ____ _ _____________ ______ ________________

____________________ ________________________________ "_-_'0__5_,0@ '_$1_____5_+_$__2__7-:__'__8_$________

"_ _ __ ____ ___ _#_ ______ _____ ___ ____ __ _(___ __________ 7E8_ ___ ____ __ # _ __ ____ " _____ ___#______ _____________ "_________________ __7____-:__'_$8_$_

________ __ ________0___ __ __ __ 2___ ___

_ __ __ 2 ____ _ _ ___N____7;8_

_7__O___8 &_"_2_'2_$01$


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OHO

t-Bu2MeSiClEt3NC5H11CHOJ78 PNO2

ONO Si MeButButC5H11NO2Bu4NF, THFOSiMeButBut69% (de: 95%)7'__8NO2CH3CF2HOH

39 THE NITRO-ALDOL (HENRY) REACTION!__ ______ __________ ____ ___ ________________"_____ __ ________ _______

__________________"_____ ___________ _____0_"_______ __7_____ __.__8___ ___ __________

____________________ ________(__________ #___ ________________E_$1'__E_$1'____ ____


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CH3CH3OH OHNO2CH3Al2O3BI, 24 +

69%7'___8PhMeOHNO2t-BuMe2SiClTHF,5 Et3N, Bu4NF3H2ONO295% (erythro/threo = 53/47)PhCHO +7'__8

O ONO2O ONO2C6H13OHHOH NO2HOTHPOOHHO2NOTHP

OO

n-C6H13CHOAl2O386%BI, 24 ++1) NaBH42) H+Al2O3CH2Cl2,40 P64%53%7'__$87'__'8

AcOH, THF C5H11NO2OHJ70 J60 PJ90 P(de: 62%)NO2BuLi, HMPATHF, 90 PN


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O OLiLiNO OLiC5H11OLiC5H11CHO7'__83.1 PREPARATION OF-NITRO ALCOHOLS3;

_______ _________________________" __#_____#___________ "_____ ___ __________________ _____

_____________" ____ _ #_______________ __ ____7-:__'___8_________ __ ________ _________ ___________ ___ _____________#_0_1__________________ "_________________ ________ ____72_E2_8__________ _______"________2_E2__7____

_8_______ _____ _____ "_____ _______7____ _8___________7____

_8____0_1___$__+_7____=8____ _____________________ _______________" __$%'_______ ________ _#__________

_______)%_;______2 _____________________________ __________ ____________ _ ______________ _______

______#___7-:__'__.8_$)____ ____ __ __ ______ __ _____ ___ ____ ___ __________ _ _ _______ "___ ___ ___#_________ #_____ __ ____ ___ _____ "___ ___________#_ __________ _

"_______________________________________$)0___ ________ ___ _________ ___#__ _ ____ _______ _ _ #____ ____ ____ _ ___ _ __ _________ ___ ____ ____2___ __ __ ___________________ _________ _#_____7____

______8_____ __ __ ____._%_,;______ ________________ "__ _______ ___________ __)"___________" _____ ______ ________________ _______#____________#________7_+8_____________7-:__'__)8_______ _#____ __

________________ _(___ __________7E8______ ____""____________________________________

____7___

-:__'_$8__ _______'_ __,__________ __ __ _____________________ _____ ___________________ __ ___

E___ _#__ $__________ __ __ ___ ___ _ __ ______ _____ ____ ________ _____ ____ _______ ___

_ ____ ___________#________________"__ _____ ______________________ ____ _______#_______

____ ____ _ ______ ____________7-:__'___8_$_NMe3+OHOHNO2ROHNO2R

OHNO2ROHNO2ROHNO2RNOH


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NO2RMeO O2N F FO O OMeO O2N F F NO O OR-CH2NO2R: Me, Et

7'___8CHONaOH, CTAClNO2HO(CH2)6H2O, RT, 3 h OHHO(CH2)6CH2NO275%+7'__.8O NHMe2N NMe2HONO2BI, 48 71%CH3NO2+7'__)8A-21NO2HO(CH2)6OH20 70%HO(CH2)6CH2NO2+ CH3NO27'__,83< THE NITRO-ALDOL (HENRY) REACTIONE_ _________ _" ______ ___#________________ "_____ __ __ _________

___________ _______ _ ____ __ "_____ _________!_______________________ __________ _____""

_______ ____ _ _____,%.;______7-:__'___8_'_ _(___ ___________7&02_$2_$8'0_________""________________" __________________ _________ ______ ____#________ __ ________________ ___________ ___________

_________ ________7-:_'_$8_$_E___________ __ __ ________ ____________________ __ "___________

_____________ _______________________ "___$_____ _______7___ _;8______________5_________ ___________

___________ _______#__ _ _ ____ __ ____________ _________ ____________ _ _ __ ________ _____________ ____7-:__'_$_8_'_

!"__________________________________________________________ __ __ ________ _________# _______"_ ___ ___________________________ ____7-:___'_$$____'_$'8_'$7'_$$8ONNNR P RNR


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MgSO4, 7 hHONO2cat.+ CH3CH2NO282%

7'_$8O HONO22 BuLi, HMPA65%THF, 90 PNO27'___8OH2NCH2CH2NH2NO2MeO MeOCH3NO270%

+7'_$_8O HONO2MeMe9 D*, 30 P50%Bu4NF+ CH3NO27'___8OR NO2H2NCH2CH2NMe2

R NO2benzene,80 P61J99%+3.1 PREPARATION OF-NITRO ALCOHOLS32 _G_#________ ______________ ____(________________ __ __ ________________

____ ___&_____ ___ "_____________ ____ _ _ __ _________ ________ _____ ______ _ ____ ___ ____________ _________________ ____ _ ___7-:__'_$,8_''____________

_____________"___" __________#____________ __ __ ____5___________ _ ________________________ _" ________________ "_$_,_________

_( ___ _______ ______________________________ "_____ _( ___E_',_2 _______ __ "_________

________________'_$________ _____________"" ___________ ____ _ _____._;_______&__________(___

__#________ _____ _______ __ ___________ ___ __ _________ ____ _______________________7_5_8_____________ __________#_ ___________ ________________&_____ __ "_________ _#_ ____

________________ ___ ___ #_____ __ ____ &_____ ________ ____ _____:_____ #___ __ ______#__

_____ 0_!1,


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" __ ___________(___ __#_________ _( ____________ _____#_"________ _(_________ _( __

____#_78_#__________________ _( ___7_______'_$8_'_31 DERIATIES #ROM_4NITRO ALCOHOLS31/ Nitro(l*enes

>_______ __ "_ ____ ____ _ _____ ___________ __________ _ "_______________ __ "

____ _________ 5_______ _ ____ ____ ________ _____ ___ ____ __________ _____ ___ ________$____ ___ __________ __ ______(____________________________"________________________"_____________ ___>_______ ________________________ ________ ________________" __ _____ _ ____ ____ ________ ,$_,'_ _____ _ ____ ____ ________ _____ _____ _______ ___ ________#_____" __+_____________ ___ _____ ______________>____E__________ ________________NO2Et3N OHHCHO NO280%+7'_$,8NO2CHONO2

OHNHCHOOH OTBSOHNOOTBSNOOTBSINOOTBSON61% (ds = 5.5:1)Dabco2) H2/ Raney NiO3) HCOCCH3O1) NaIO42) Ph3P, I2BuLiI2NO PhMe3SnPd(PPh3)41) O5O4

S)hee 31 Model studies on the synthesis of hennoxazole AORH2NCH2CH2NMe2R NO2benzene,80 PCH3NO255J80%+7'_$'8


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3? THE NITRO-ALDOL (HENRY) REACTION___________2________,________ _______________ _____________________"______#________ _#________________________________,$

_____________>_______ __ "_$____ _____ _,,_____#__________________7_;8______________ ____ "__________ _9,'____'_%'__2O______#_

______ __________ ________ __ ___ ___ ________ ___ _______ __ "_ $_____

__ ___ ________________________7)';8,__ ________________E_10_

,.9_____.%_)2O_____#_

_______ __________ ________ __ ___ ___ ________ ___ _______ __ "_ _____ $__ ___ _________________" _______ _____________________7';_____8_,)______________E_10__ 7__;_ ____8_,._ ___________ ________ 7__;8,_9_ ______2O'____#_7-:__'_$_8_>_______ __ "_ ____ ____ _ ______#________________ __________" __

___#____#______________________,,_ 2_'_1$2_-_'0_,)_ _____ __ ______ ______ 7>228_,__ E_$1E_10___ _'22_,_,______@EE-_'0_______ _____"______-:___'_$.,_____'_$),)__>_______ __ "_ ____ ____ _ _______#_>22_#_________ _____ "_________

________,__________7_8__ _________ _______ _____________________________ _____ "__________________ ______

__

___________ _______ 7_8_ 7-:__ '_$_8____/____ 7_8_ ____ ________ ____ _______ ____ ____ __"___0___ ______O____ __________ _ ____ _____%)__2_" __ ______ ____

________$1$_#____7_8____ ________7-:__'_$_8__$O2N RHOOOO O2N R140J180 P80 CR = H (80%)R = Me (73%)7'_$_8

OHn-C4H9DCC, CuCln-C4H9NO2NOPhO CHOAnNOPhOAnNO235 P, 10 90%NO285%

2) MeSO2Cl, Et3N1) CH3NO2, Et3N7'_$.87'_$)8n-C3H7MeNO2TPPMe MeNO2


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PhSeNaAcOHNO2MeMeSePhMeNO2

n-C3H7H2O2Me NO2Me70 % (anti/syn = 91/9)20 E/Z = 55/45 100% (E/Z = 100/0)J78 P99% (Z/E = 90/10)7'_$_87'_$_83.2 DERIVATIVES FROM-NITRO ALCOHOLS3=E_$1'_____________ _____________" __________________ __________________#__#__________

____ ________ ____ _______ ________ ___ __ __#_ "_ ________ ___ ____ ________ _____E_$1'_ _______:___________#____,_2_7-:__'_'8__'!__ #________ __________(__ ______ ___ "_ __ ______ ________ _____ ____ ________ #_______ ________ ________ 7______________________ __#___________________ ___________#

___________ ______-:___'_'_%'_',__,%__!______ "_____#_____>______________________________ ________________ ________"__ _____#+_0_'2_OE_1


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MeNO2OMeCHOMeNO2MeO

MeOOMeMeO++ CH3CH2NO2O2NBrCHOCH3CO2NH4CH3CO2H

+82%NO2NO2O2N NO2Br Br

7'_'_87'_'$87'_''87'_',8MeOBzOMeOBzOCHOMeNH3Cl, AcOKHC(OMe)3MeOBzONO2

OMeOBz77%MeOH,T+NO27'_'_898 THE NITRO-ALDOL (HENRY) REACTION"_______"_ ____________ ____ _____________________.__/____________ "_______________#___

________________ __"_________________________________#_____ _____ "_______________

___________2________________ "__ _______7-:__'_'.8_E________ __ "_________ .$_ ______ _____ ________ _.'_#______________________ _______

_

______ ___ ___ __ ___ ___ -:___ '_')_ ___ '_'___ ______________ _______#_ ____ ____ "_ __>______________________________&_____ ___ "____________ ____________________________________2_,___________________"" _____ ______________.,_______________________________ __ "_____ ____ _____________

______7-:_'_'_8_._0___ ________________"_ ____ ________________________________"___ " ____________ ______________@ ___ _____________ __________________ __________ ____

____________0_"_______ _


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7_____ __.__8_ ____ ____7_____ ____$8_______________ ___ ___________________7_______._'_$8_

_____________ __ "____________" _____ ____________________9________ ____ ____________________ ________(_________________________'_'____'_,_____________________ "___.____ ___ __.._________ __________ ________ __.)__________________________ _ _______________ _________________ _____#____#_____$____ $__ _____$_$_________ ___ ____708____________ __ "_____ _____________" _________#_______'

____ _$____ __ __________;____________:____________ _________ __:__________ "___________ ________________ __ "______________"" ___0____________ _____________

____,__ _$#95%Envirocat EPZG100 P, 20 + NO2CHONO2Me7'_'.8OMeMeO CHO

OMeMeO NO2NH4OAc/ AcOH100 P, 3 Q? (%)35CH3NO299NH4OAc/ AcOH22 P, 3 , ))))+7'_')8CHOCl NH

FR*A400 U8 64%+ CH3CH2NO2MeNO2Cl7'_'_8NMeCHOTiCl4O N Me NMeNO2

CO2

MeTHF,0J25 P+75%O2N CO2Me7'_'_83.2 DERIVATIVES FROM-NITRO ALCOHOLS9/______ ____ ___ __ ______ 7-:__ '_,8_.__ 0_ ___ ___ ___________ ____ ____ __ "_ __

_ _""__________ _______0______0_$______ ______-:__'_,________ ______ __ "_____________#___ ________


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____ 0_"_ ______ __ __ ______ __ ___ _ ____ ___ _ __ _____ ______ 0_ __ ___"______#____ " __ ____#____________________ ___________-:___'_,$____'_,'_MeOOMeNO2NO2

MeO NOMe MeMeO NOMe MeNO2MeO NOMe MeNH2CHOOHCOOSiMe3

MeO NOMe MeN H

H MeO NOMe MeNHOO

Oi-PrOaspidophytine1) Fe, AcOH, silica gel,toluene,2) MeI, KOH, Bu4NI,THF,23 P1) POCl3, DMF, 35 C,1 h, then NaOH aq2) MeNO2, NH4OAc,, 1 hLiAlH4, THF,, 1 hMeCN,23 P, then TFA,0 P, then NaBH3CN,23 P67%91% 88%66%S)hee 39 Synthesis of aspidophytineCH3NO2HCHONO2HO OHNO2t-Bu O O t-Bu

O OAcONaNO2O t-BuONPP1) MeONa/MeOH45%75%2) Salicylic acid+t-BuCOCl


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7'_,8HOHOCHOCH3NO2HOHONO2HOHO NO2NO2NHHOHOC(NO2)4, ZnSO495%70%Na2S2O4, ZnSO4NH4OAc-AcOH EtOHpH 4

52%S)hee 33 Synthesis of 5,6-dihydroxyindole91 THE NITRO-ALDOL (HENRY) REACTION2_______________ _____#_ ___#_____ _____ _____ ________ ___ ______ _______________ "

___________ __________ ___ __"_______ "_ ________ "____ $____ ____ __ _____'_ ___7-:__ '_,,8_______#________________7=-8_._________ __ ________ __" __ _____________ __#_____$____

__'____________________"_____#_____" ______ ____ __7-:__'_,_8_)7'_,'8NPPNO2Nu1

NO2Nu1Nu2ONu1Nu2NH2Nu1Nu2LiNPPNO2OEtOLiNO2OOEtNH

H2/Ni82%88%ONu1Nu2NefReduction66%THF, 70C THF, 70CEt2O-EtOH7'_,_87'_,$8


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n-C4H9LiNPPNO2OLiOO78%1) MeONa/ MeOH

2) H2SO4ONO277%75%THF, 70C THF, 70C

AcO OAcNO2HO OAcNO2ONO290% (95% )1) Piv2O2) MeOH/H+3) DCC/CuClt-Bu

O67%PLE7'_,,81) HCHO, MeONa2) PhCOClheat65% (A*??)CH3NO2OOHNO2OTHPNO2

ONO2PhONO2OMeONa H+7'_,_83.2 DERIVATIVES FROM-NITRO ALCOHOLS93________ __ ______ ___________________" ________________ "_$_$_________________

__________ _ _ ____ ______________ "_ ____ ______ __ _____ ___ ____ ____ ____ ___ ___ ___________E___ __________ __ ______ ___ ____ ____ " __ ____ _________ __ "_ _____ ____

________ 7___2_______,8_311 Nitro(l*(nes&_____ __ "_____ _____________0_5_,____________________" ________________ "_____ ________)__ !__ _ ___ _______ _ _______ ______ __ _____ "_ _______ __ _____ ____ ___ _ "

________ _#________" _____ __________ _______________________#________ ____ ___)$________#________ __""___________________#__________(___ __ "_____ __________$E________ ___________

_______________:_______________________________ _______0_5_,_)'_______ ______ ______________ _____ ___________________ "___ ___________________ _

#______________),_E_______


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___ _""_______ ____ _ " __ ____ ___#_______ _________ __ "_ __________ ________ _________ ___ _______________ ____ ___ "_____ ______________,_ ____________ _____""_______________________ __ "_0_5_,________ _____ "___,_ ____________ __7-:__'_,.8_)_____ #_____

_"_____ ___________________________7___________ ______8__ _______ ____7/______ _

________8_#________ _# _______ "___ _____).

__________ __ "_____ _____________F_5_,______$_____ ________7>+-8_#__________ _____ ___#_ _____ __ ____ ________ ______#_ __ ____ __________ "_ _______________________

____ ________ ____ ______ _ _ ____ ______________ __ ___ _____#_ _ ______________ _""__ ___

____ ________7-:__'_,)8_))4____________________ __ "_____ ___________ ______ _____ ___#_____

_______________________#0_205_'_________________ "_____(_______F_+____________ __7-:__'_,_8_)_0___ _________ __ "_________________________ ________ ____ ____ _______

_______#_ "________________ ____________ ____________ ________ _____ _ _______________

_______#____ _" _______________ __ "______ _________.__)__!_______________ _______________ _"_____

________________ _______ ________ _______________________ "_+E8__________________________ ____ ________ __________________ ___"_____ ____#_

______________ "___NO2NO21) NaBH4, dioxane-EtOH30 C, 1.5 h95%2) AcOH7'_,.8MeO NO2MeOZnBH4MeO NO2DME MeO86%7'_,)8ONO2ONO2NaCNBH3Zeolite H-ZSM570%7'_,_899 THE NITRO-ALDOL (HENRY) REACTION_________________________ "___________ ______.__&_______________________. __ __

_____________ __________ ________) ______ ____________ _________

__________:_____0_"_______ _7-:__'_,_8_)___E___ _____ _______ "_______________________"________ ____________ ___________-:__'__%'__$_______ ____ _ ___ ____ ______ #_ ____ ___ ____ __ _____ ____ "_______ _ ______________ ___"_____ ____#_ ________________ _________ ___________#_

_______________________2_______.__


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1) CH3NO2, KF, i-PrOH3) NaBH4100%NefCO2Me 2) Ac2O, DMAPCHOCO2Me CO2MeCHONO27'_,_8O NNNNO ONHBzOPh2CHOOHNHBocO NNNNO ONHBzNO2Ph2CHOONHBocOO OOOOAc NO2O

AcOAcOOAc O OOOOO NO22) Ac2O70%3) NaBH4, EtOH1) n-Bu4NF, THF,18 +71%1) KF3) NaBH4

CHO2) Ac2O, DMAP+OAcAcOAcO OAcO2N O NNNNO O


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NHBzOBnOOHNHCbzO NNNNO ONHBzNO2BnOONHCbz53%1) KOt-Bu, t-BuOH, THF3) NaBH4, EtOH, THF+2) Ac2O, DMAP, THF

O2N7'__87'___87'__$83.2 DERIVATIVES FROM-NITRO ALCOHOLS9;&_____ __ "______ ______________"________#_5______________ ___________ ____________ _#____ ____________________ ________7-:__'__'8___313_4Nitro @etones0___ ____ ___________"___________________ _#____________________________#_________________________________ __ "____ ____72_______$__8_ _____ ____ __ "_____ ____

_ ____E______ __ "____ _____________________( ____ __ _____________#____#___________ ________________

_" ______________ __ "_____ ____ ____7____2________8_7-:__'__,8_

!__ ___________________________ "_____ ____ _______ _______ _________ __ "_____ _______7____________ _8_" __ ______ ____ __________________ ____ ______ ___________________

_______#_ ________ _ ___ _ ________2_1'_ __0_$2_$1)_ ______ _#_ ____________$_____ _______

_ ____ ________________ _ ___ _____7228_'_ __


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_""__________2________#__#_____ "_____ _____________________ ____ __________________#

MePhNO2Me HPh CH2NO2Baker's yeast50% (98% )7'__'8OMNO2OHNO2ONO2OX+oxidationoxidizing agent

CrO3, Na2Cr2O7,PCC, etc. NO2X(X = Cl, OAc)(X = N N )7'__,8PCC78%12 OHO2NO OOO2NO O

OH CH2Cl2,10 C, 2 hMe NO2OMe NO277%K2Cr2O7,30%H2SO4n-(C4H9)4N+HSO4-7'___87'__.89< THE NITRO-ALDOL (HENRY) REACTION_______)_E___ _#________ ___________________ "_____ _______________________

__#________________ _____________________ ___ ________ __________ "_ ____ __ __

___________5_1+_1______________ _#________________( _____ _#________ ____ _______.%_;______7_________

____$_E______ __ "_0___ _2 __ ___8_7-:__'__)8_ __________ _#_ ___ "_____ ____ _________________

____________________________5_'______ _______ _______=_E__,_ "______ _____ ___#__ _______(____7-:__'___8___>_______ "_________

_____ ________ ___ _____ __ )_$__ ___ _ ___ _________ ___ "_ _____ __ _____ ____ __ _____________


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'__%'_)_2 ________ __ "_ ____ ____ __ "_____ ___________#_ ____ _________#_ __

______ "_ ____ ____#_ ___" __ ______________ ____ __________"____ __" _______________ __

"_____ ____________ __________ ___ ___________'__%'_)__@ ___ _______7_8G___ __________ G___

___

_ ___________ "__________________ "_G___ ___"_ _________________________________________'______________'_.____'_)_____________________ "_____ _ ________________ __ "________ _____$__'NO2O OO O NO2n-C6H13n-C6H13OONN2)1) t-BuOK/ DMSO

88%7'__)8O O NO2OH RO O NO2ROTsNHNH2O O NO2RNNHTsLiAlH4O OR

NNHTsROOOHOR CH2R =R =(CH2)4CH32) K2Cr2O71) Al2O3+H+acetoneS)hee 3;

R1OR2NO2Bu3SnH, AIBNR1OR2R1NNHTs


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R2NO2LiAlH480 PTsNHNH27'___83.2 DERIVATIVES FROM-NITRO ALCOHOLS9319_4Aino Al)ohols0___ _ ___ _ ___ ________ ___ ____ ______ ______ __ ____ ___ ______ _______ ___ "

__ _______ _ ______________ __ "_________ _#_ ____ _________ _"_____ ______

__ ___________ ________ #_____ __________________ "_&_____0_____-_1__ __O2______@____+_1__7________ __,_$8_______ ______ _____ _____ ____ _ _________ _____________________

___'_$_____'_'_31; Nitro S0+(rs (n% Aino S0+(rs___________________ __________ "_____ ___#___________ ___#____________________ ______________________ ____ ____ _ __ ______ "_____ ___ ______ ____________ __ _____ ________

_ #____OH3C HNO2

OCH3ONO2OCH3OH OPCCNO2OCH3O OOCH3O OOCH3O OSCH3OCH3O OOHO O71%1) NaIO471%1) (CH2OH)2, H+2) LDA,J78 P3) (CH3S)2, HMPA,0 P4) (CO2H)2+80%86%amberlyst A-2186%2)100 Pbenzene

Bu3SnH, AIBNCH2Cl2S)hee 3


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TsNHNH2MeOHC5H11NO2(CH2)9CH3NNHTsLiAlH4C5H11(CH2)9CH3NNHTsC5H11(CH2)9CH3Oamberlyst A-15Me2CO/ H2O95%+1) amberlyst A-212) K2Cr2O778%90%THF,0 P90%S)hee 3

9? THE NITRO-ALDOL (HENRY) REACTION____________,___________ "_____ ________ ___#_______ ___ "______ ______ _______________

___ "____ __ __ _ _______ ___ __________ "_ ____ _ __#____ ____ _____ _____ ________ ___/___ ________ _ ______ ________________ ______ ________________ ________

_____._1____________ _____________ ____ ________ _____ _ _ __ __ ____ ___ _______ "_ ____ __ __ ______ __ _______ _____________________5___@________ _________ ___ "___________________ __________ __"

__ _______#'_ _'____ __ _____ _____ ___ '____ '_ ___ ___ ___________ ___ ______ "_ _______________ _________#_______________#________________ __________#___ ________#__ "#___ _________.___________ __ "_____ _______________#_________________ ______-:__'____________(___________=#___ _____ _____7_6_8___" _________________ __ "_____ __________________#___________ _______"_ __>#___

_________ _____ ____ _________ ___ _ _______ ___ ______________ "__ _ _ ____ _>_ ___=__#____7-:_'_._8__________ __ "_____ ___________________ _________ ____"_____ ___

"___#__________________"________#__" ___ _____ __ "_________ __________$E______ $_ _>#___

___7_______>#___ ______8____________ ____________ "_#___ __ ___________ _______ ___"_____________ _____

____ ______ ___ ____________#__" ______ _____ __________ "__#___ _____ ______________

_______ _"_____ _______7-:__'_.$8___XOHCOHCX


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+OHNO2HOMeNO2KFi-PrOHX = O, S7'___8HOOHOHOHOOOHCOHCOOOHOHO2N

OOXH2NOHOHHOSeveralstepsMeNO2NaOMeMeOHNaIO4X = SMe (mannostatin A)

X = SOMe (mannostatin B)7'_.8OHOOOOMeMeHO OMeO2NHOHOOMeHO

HOO2NOMeOHMeHO OMeO2NHOFOMe


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FHOO2NOMeOHEtNO2NaOMe +7'_._83.2 DERIVATIVES FROM-NITRO ALCOHOLS9=!"_______ _______________ _____________ _#_ ____________ ______#_____ ____

_________ ___________ ______________" _______ _____#_ "___ __ _ ________________7_________

__'_$_$8___________ _ ________________________ _" ________________ "_______

___________#___#_____$_E_________ _____________________-:__'_.'__$_'0___ _ ___ '____ _ __#____ _____ _____ ________ ____ _________ _ ________ __ "_ ________________ ______________ __ ________#_______ _____________'____''E___ $_'_.____ _ =__ ____7E>___________'__8_ ________________" ____#_____#___ ________ "_____________ _________ _________ ________________

_____________,____________ ___________ ______ __ __" ________________ "________#_____________

___ _____E____________(________ __ "________'____ __ ___ _____________(__>___________#_____ ____>___ ____ __ __7_____________ ___8____.';_____________ ____

_______ ___ _ =___ _______)_____ 7____ _____ __'_'8__ _#_______ _ ___________ ___ _______ ___ __________ "_ =__ _______ _____ __ ____ _____ __________ ____ __ __ ______

__ "$____(__=___________ _____ '____ __ ______ ________ _______ ___ __ ___ ___ ______'____.__________ ______________ __ ________ ____________ ____________________

_________ ______________________ __'_'_HO OHOOHNO2NHAcHO OHOOHCHONHAcHO OHOOHCO2HNHAc

HO OHOOHNHAcNO2OHHO OHOOH


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NHAcNO2HO OHOOHNHAcNO2NaOHH2O, O3+MeNO2NaOMeMeOHAc2OH2SO41) H2, Pd/CAcOEt2) NaOMeMeOH7'_.$8O

OOMTMO CHOOOOOOMTMOO2NO NO2OOH

+KFi-PrOHMTM = CH2SCH37'_.'8XONH2(NO2)OHOHROR NO2O

XOHR = H, Me X = H, OH+S)hee 3?

;8 THE NITRO-ALDOL (HENRY) REACTION33 STEREOSELECTIE HENRY REACTIONS AND A!!LICATIONS TOORGANIC SYNTHESIS

0___ ____ _ _____________ #_______ ______ _____ ___#_____ ____ _ _______________ __ "


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_ _"_#_____ _9__________ ______________________ __________"____ _________________ __ "_______

_ _ #__________ __________ ____ _ ____________________#_____________ ____________

_ ______________ ________ ______ __________ ____ ________________________'_____)

!__#________________________ ____ ___________ ________________ _#________ _____

"___________ _____________ ____ ______E_______ __________ ___ __________________

____##________"________ ________ ___7_ ____"______________ __8________________________________

_________________________ ________ ______ ________________________ ______ _______________

"_____________________ ____ _ ____________________ ______________________ ____________________________ _ ________________________ _______________#_______ ____ _

________G ____ ____7-:__'_.,8___CH3OH2N

HOHOCH3OHOHONH2CH3OH2NHOOHCH3OHOOHNH2O O OOMeO OHOHROOHNH2OHL-ritosamine

(L-ribo)L-acosamine(L-arabino)3-epi-L-daunosamine(L-xylo)L-daunosamine(L-lyxo)daunomycin (R = H, 4 -OH)adriamycin (R = OH, 4 -OH)


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epirubicin (R = H, 4 -OH)4

A B C DS)hee 3=

OOR[Si]O2N OMe

OMe OMeOHNO2OMe+0.1 Bu4NF("anhydrous")THF,78 to3 C, 14 h RO*. 60% (: 29:51:3:12)1) separation2) H2, Pd/CL-acosamine82%S)hee 3/8

3.3 STEREOSELECTIVE HENRY REACTION S A N D A P PLICATIONS TO ORGANIC SYNTHESIS;/

____________ _ _______________ ____ ______________ _ _ ___" _______ ____ __ "________________ __7_______'__$8______

+____ E6_ _> _____ ___ _ _____ ____ ________ ______ _____ ________ _ _ #___ ________________ ________ ____________"" ________ ___ _ ________G

____ ____7__6)%,)6'8_ ___ ________ __ _ ____ __ ___%__ 2_ _____@_+E__ ____ ______ #______ _________ ___ _ ___ ________ 7_+E8_ _______ ___________ ____ _____ _________7>+8_

+____ 56_ !__ _ ________ ____ _ ____ __ "_ ____ _______________________ __________ ________ ___#__________ _________________7,_6_%__6_8_

+____26___#_______________________ _ ______________"__ _________(________ __"

__________ _______________________________________ _____________________# _____"_ ______________ ____________ ____________________________________ __ ___________________________ _______%)__2______@__________________________#__ "________________ ______________________________ "____________ _____ "_ _____________ _____ "__ ____ 7_5E@8_ _ _ #____ ____ ______________ _______

"________ _ __________#_________________7__;8_____________ ______________________ ____________(__________'_$________ ________________ _____ ____ _

_______#_&_____0__$_____________ _"______ _"_#_____ __ "_ ____ ____ _ ___7_______'__$8_

________ ________ 7__8__ ______ ____ _____ __ ____ ___ _____ ___ ______ _ _ _______

_____ ____ _______________________ ________________ _________ __________#____________ _ ___

O2NOHOHNHCOCHCl2OHNHMe OHN NSO2


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OOHNH2HONH2OHNHHO OAc OMePhOHNH2OHO (B. 107) ???* (B. 107) (B. 107*)C (B. 107)(-EV) (B. 107)?*? (B. 107*)S)hee 3// Biological active-amino alcohol derivatives

OR1HR2NO2

OHR1R2NO2OHR1R2NO2HR2NO2R1H OHHR2NO2

R1+ HO H+anti erythro syn threo

7'_.,8;1 THE NITRO-ALDOL (HENRY) REACTION___ _____ ____ ____________ _ __________________# ________"____________

__ "__________________ __ ____#_________________ ___________ _ _______"___________#___________

____________7__)___ ___;8__5_______________ __ ____________(___________________________

"____#_________ ___________________________7-:___'_._____'_..8___NO O

LiLiONO2EHO R C+OHHR C+


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OE+= , R+ ,2) H+THP1) E+7'_._8

RO HNO2LiLi RRRNO2LiHXTHF-HMPAAcOHOHRRNO2OLiORRNO2RRNO2LiAcOHOHRRNO2

Bu4NFORRNO2+HORNO2RRCHOF RCHOJ90 PF Sit-BuMe2OSit-BuMe2NRMeJ90 P 2t-BuSiO OLi


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LDAF J70 P100 PNR OO

Sit-BuMe2Sit-BuMe2DMPU = N NOH3C CH3S)hee 3/1

C12H25C Cp-MeOC6H4-Ph-687993O NO274THP

>9580HO R91NO2OH1) n-BuLi, THF-HMPABMe2CHA*??? (%) (%)752) RCHO, H+7'_..83.3 STEREOSELECTIVE HENRY REACTION S A N D A P PLICATIONS TO ORGANIC SYNTHESIS;3____ __ _____ ____ ______ _ _ ____ _ _ ___ ______$&_____0__ ___ _____ ______ ___ _ ___

"_ _"_#_____ ___________7-:__'_.)8___

5________ ___________________ __________# ______ ______________________ ___________(_______ ___ ____ _________ "_ "__ ____ _ __ _ _ #____ _______ ____________ ___ # _ __________ __#________ ____________7__;__8_7-:__'_._8___OHOHNO2MeOH2OHOHNH2MeORaney Ni98%7'_.)8

___________ ___________________________0___ __ __ __ E_____ 2 ____ _ _ ___ __O___

_8_$_5_=______ _ __@_+E __O___ _ $8_E_1___%__2_ _ _7+___ _E8_8_$_5_=______ _ __@_+E_O__ _ $8_E_1___%__2_8_$_5_=______ _ __@_+E


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_,O._ _ $8_E_1___%__25_,0@_

_7+___ _28_O__5_,0@ $$O)_

_E_1__

_7+___ _58_O__E_1_ _O__

_E_1_ __O_$CH3CH2NO2C5H11CHOCH3CH2CH2NO2PhCHOCH3CH2CH2NO2MeO CHONOH CH2CH3

C2H5CHONO OH CH2CH3C3H7OC2H5NO2LiC5H11OCH3NO2LiPhOC2H5NO2LiCHOOMe2t-BuSiMe2t-BuSi

Sit-BuMe2Sit-BuMe2Sit-BuMe2

NO2C5H11OHNO2PhOHNO2OHNO2OC3H7OC2H5NO2C5H11OC2H5NO2PhOC2H5NO2


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NO2OOMeSit-BuMe2Sit-BuMe2Sit-BuMe2Sit-BuMe2

Sit-BuMe2;9 THE NITRO-ALDOL (HENRY) REACTION__________ ______ "_$_$_$___"__ _ ____ __________________________________________

"_5_,0@_____@__ _#_________________ _____ "_____ ____ _ ________

______-:__'_.____________________ ________________________ "______ ______________#_" ___ _"__ ___________

#________________ _ ____ __O____ _:__________ "_ 2@'__________________ ____ _ __ ____ ____ __________ _________"__ _ _______________________________________ ____________ _ ____ __ "______

_____ ___#___________________ ______7-:__'_)8____E___ _____________ _______ __ ______ " __ _____ ____________ ________#_____ ____ _ ______

_________ __________________ _______"_______________ __ "______________ __________________@__ ____ ______________________________________ "___ __ _ ________________

________ ______________ _#____________ ____ _ ____________________________ __

_____7-:__'_)_8___$_________ ____________________"___ " ________ __"_________ ___________________ _______ __""_________________________________ _________ ___:______ "__ ____________ ________

__E__________ #___ _____________ _______________+#E_____ _________" _____________

___________________ "_ ____ _ ___ _ ____ ____ _ _________ ____#__+#E__ _____ ___

___ _______ _______#____________________ ________ _________#________________________ __

"____________________5 _____ __________________________________________ ____________#________________

_#___________ _ ______# ________>_______ __________________ ________________

"______________,____ ___(__________$___ _ ___(______________________ ________ _#_________

_____ ___#____ _ ___ _ ___ ___ _;_ _________________'_ ________ ____ ______ __ _____ __________________ ________ ______________7-:__'_)$8_NOMe3SiOH

PhOBu4NFOMe3SiOHPhPhNO2


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86% (95% ds)PhCHO7'_._8Bu4NFi-Pr-Php-MeOC6H4-

F3C NO2F3C HNO OSit-BuMe2B Q? (%) syn/antiROCF3NO2Sit-BuMe2527272

76/2475/ 25OC6H13CF3NO2OC6H13CF3NO273/ 27RCHOanti/syn = 93/72) AcOH,95 P

Sit-BuMe2Sit-BuMe21) LDA7'_._87'_)8O2N CHOTHF, RTOHNO O2 2N

1)n-BuLi72% (anti/syn = 7/1)+ NO2

2) TiCl3(Oi-Pr)7'_)_8

3.3 STEREOSELECTIVE HENRY REACTION S A N D A P PLICATIONS TO ORGANIC SYNTHESIS;;_________ ________________ ____________________ ____________________________________+______

____ __ "_ _____ ___ _ _____ _______ ___________ _ _ __________________$____ ______" __ ___________:___________ ____________ __ _______(___ ________

____________ __________________ __ __ ____________________________ ____1__#_ _________________

______-:__'_)'___,___________ _____________ _______________ "____ _$___ ___ ________ ______-:__'_),____


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!__ _ ________ __ "_ ____ __________ "_ ____ _________ ___________ _____ __________________ __________ ___ _________._________ ______ "__________ ____________ __

_______(___ __________#_ ___________________ ____________ _ _ _____ "_-:__'_),_ __________________ !___ _____________(___ __ "_-:__'_),_____________________ _ _______ __ _______(___ ____

_____________________ ____________________'__'___ _____________ "______ ______________ "____ ________________

+_______ ____ __ "_ ____ _ ____(____ ___#____ ______ "_ __ ______ ,__ _ _________ _ _ __

__ ________)_" __ ________________ __________ ____________________7>!5E=_8_#__________:___________ ___________________________________" ____________ ____________ __ ________

______ _________ _ ___ .__ ___#_ ______ ________ ____ __ __ _____(___ __ __ ________ __ __#__________ ___________________________ __ ___ ______________________ _______________G

____ ____________ ______ _________ _ _"_#_____ __ ___ ______ _____ __ ______ ___ __________ ____ _______________ _______ "_______ ___#________1____ ____ _____ "_________ ________ _ _________________ ___ ____ ___ ____ "____ "___________________________________ _______________ __ "___ _________._____&_______________________

_ ______________ ___________________ ________________________'__,___ ____________ __ "_

_______________=__________ __75!01=8____________________""________________#____________________ __

_______ ________ _____________'_______________ ___________+_+$___ ___ ____ ____ _____________________

"_______________________________________ _____________'__._____________________ ______ "__________________

__7__#__=_'__E_'____'___'8______________________ ___7__#___=___0___


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OO HTHFOOHOHONO2OONO2OCH3O O OTHFOOOOHCO2CH3

HNO2OO NOHH+55%A*?+58%7'_)'8

7'_),8;< THE NITRO-ALDOL (HENRY) REACTION___ 7 8_ _____ 7_8________ ____________________ _______________________=___________

_________________________________________ _________ ____________ __ ____5______"_____

____ "_______________________ _________ "_ _#___________ _____________(___E______________ __ ________

____________(_____ _______ ________5!01=_7==58____$_ ___________+_______ ______ ___ ____ ______(____________ __ ____5!01=_7=_58__$$_______________ __ ___ ______ __

"________________(____________ __ _______5!01=_7=58__$________________+________ ________

__OO NHOHOHH OHOH OHHONHOHOHH OH


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OHOONO2OOEt

Br OO NO2CO2EtOO NO2CHOOOHNO2OHOOH

NHCO2MeOROOHNHOROOAlONROO

OH HAr*** (B. 116) ? (B. 116)71% (90% )81%Zn, LiI, DMF,75 P,5 ,then CuCN, LiClDIBAL-HCH2Cl2,78 P,5 Al2O31) H2(650 psi), Raney Ni,MeOH,20 P,4 2) ClCO2Me, Et3N96%Tf2O, DMAP

CH2Cl2,015 P,15 S)hee 3/3OLiOLiOHOHLaCl3Method AMethod BLa3(O-t-Bu)9+


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**+ NaO-t-BuLiCl(2 ? SA)H2O(10 ? SA)Optically activeLa catalystNaOH(1 ? SA)

H2O(10 ? SA)S)hee 3/9 Preparation of the optically active La-BINOL complex3.3 STEREOSELECTIVE HENRY REACTION S A N D A P PLICATIONS TO ORGANIC SYNTHESIS;______ __ ___ ______ __ "___________________(____________________5!01=_7E=58__$$________ __ ________ _________(________________________________(_________________ ______________ __ ________ ________(_____7 8==5_____""_________________

______________ "_ ______ _____ "_ _________ _______ ______ __ __ ____#_ __#__ 7_8___

__ _ ___$'_7_8__ ___ _ __ _$'_____7_8___ _ __$'__7_______'__)8__________________ __ _____________ "_==5___________ ___________ __ ________

_____ ____#____________________._;____7-:__'_)_8__$,>_______ ________________________ __ ________ ___ "_

_______________________ __=

______________________ ________________________ "_==5___ ___________#_____________________7___6__

W___6_8______ ______-:__'_).__$________ ________ _______________0_"_______ ______7$__'_8'

____ $___ _,___________ ___ _____ ______ ___ __ ________ "_ ____ _!4__ ______ _______ _CHOCHONO2OHNO2OHCHO NO2OHCHO NO2

OH79% (73% )La cat.(10 ?%)THF, 50 P, 20 91% (62% )La cat.(10 ? %)THF, 40 P, 41 80% (85% )La cat.(10 ?%)THF, 42 P, 2 *J50 P, 18 : 91% (90% )J70 P, 53 : 43% (95% )La cat.(10 ?%)CH3NO2(10 SA)THF

CH3NO2(10 SA)CH3NO2(10 SA)CH3NO2(10 SA)S)hee 3/; La-BINOL complex-catalyzed asymmetric nitro-aldol reactions

NPhthCHOPhNPhthPhNO2


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OHNH2Ph CO2HOHTHF,J40 P, 72 12 N HCl92% (96% : syn/anti = 99/1)

100 P, 40 CH3NO2(R)-LLB(3.3 ?%)80%

7'_).8OHCOOCH3NO2OHHONO2O(R)-LLB(5 ?%)65% 7'_)_8;? THE NITRO-ALDOL (HENRY) REACTIONS)hee 3/


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(: 80% (S)-metoprolol-: Ar =-: 90% (S)-propranolol): 88% (S)-pindololS)hee 3/ Asymmetric syntheses of-blockers with (R)-LLB as catalyst

PhCHOCH3NO2(10 equiv)

PhNO2OHi79808467cat.(3.3 ?%)')%+eh

Q? (%) (%)34567910LLB(-69748584595473

6712THF, 40 P, 91 **?86355a7179888685a6,6 -@*-EM R 93% R* .857'_))8O La OOOOOLiLiLi OHOHOHOH


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RRRRR RRR

RRLLB: R = He : R = CCPh+

( : R = Br' : R = CCSiMe3-: R = Me : R = CCSiEt3) : R = CNh: R = CCTBS%: R = CCHi : R = CCSiMe2PhTBStert-butyldimethylsilylS)hee 3/? Structural modification of LLB


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_ ____ _______ __ ______________________@ ___ _________________ __"_1___(__>______

_________________'____ __ __ _____________________ "____________________________ _____"

__________ __ ____ _____"_ ________>___ ___ ________________________________(___ ___>&__

7'_)_8

PhCHOPhFNO2OH+THF,J40 P, 96168 74% (87% )F FFCH3NO2SmLi3tris[(R)-binaphthoxide]7'_)_83.3 STEREOSELECTIVE HENRY REACTION S A N D A P PLICATIONS TO ORGANIC SYNTHESIS


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'_$$______ ____""_______" ________#_________"_________________ __ _________________5E@__'_

______:___________(__" ________________ "_________________ _____________'_$______________"________(__7_8_______________________ ________#_____________________ ____ _ ________

_)6_________ ________________________ _______________ ____,6________5E@_____________________ _ ____________ ______ _____ ___#_____ ____ _

_______0_5_,_________________ "_0_2_$_____;_ __________ _________ ________ __ _____ __ ____________ " __ ___ ___ ___" ________ ____

_____ ___(______" _______ ________ _____ ________$O2___________________7_8'_______

_ "_______ _____________ ____ _____ #_____ ___________ ___ _;_ _______ _____ "_ __ __________#_____ _____________7$__'_8___ ____ "_______________________"_ __________ _____ ____ __________ "_ 7_8______________ ___ __ ___ ___ _______ '_$$__ ____ ____ "_ __#__ ______:_____________ _________ ________ ______________'_$_____'_$$__ ___

______"_______________________ ___________ __ "_____ __________ ___ ______________

_____"______________________#__ _______ ______#_#_ ___ "_ _____________________ ______________________________#__ " _

_____ _ ___ __ "_________________ ___#_______ _ ____________________5E@_______(_______________ "____________ ____ _ _______________ _ __ ________

___#_____________________________________ ______________ "__ __ _________________

______________________________7'__$87'__'87'___83.3 STEREOSELECTIVE HENRY REACTION S A N D A P PLICATIONS TO ORGANIC SYNTHESIS


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,_ & _________ ________$_________________________5__+____ ____4 ___$____#__ ___0___N ______$___ ______#_______+__2__E__ _____________%_ _$__&___"#__'__7____8_._ ___________+___________________E_____!__&________'_________%____"___$'._7___)8_)__ 4__________5__+_________5________'_______%____________________________',_7__,8_)__ ________=__/________/__E____ ____________ _(_______"___,$'_7____8_)__ __________4___4________#____E__


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_______%%__$)_7___8_,__ _______________________)_7___$8_,__ ________E_____________-______=__&__+_____________________%(__'___7___'8____ ________________+____4______________ _______._'_7___.8_)___ 5__________5______&____+_______________________#__'___7__)$8_)___ 5 _ ____-_____@___________((___ ___ !__ _______4__+__ ____________4________ ___________,$7___'8_

___ + ______E__________+ ""________%____!_____ _____ !__.$$'_7___$8____ 5______________E__@___________2__+__________&_____/_#__________%_ _________%_ _______%___'.7___.8_

___ +_______1__&______/__=__________________%(___)._7___'8_____ 1_________0__< ____________


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___ 1_ __0______E__________________________"%___'._7___)8_____ +______&__-_________(_______>___________(__1____!______'_7____8___$_ 5________E____+___2__& ________2__>_________#________________%$___$''_7____8___'_ 5________4_____4_____>____________4_____E____________________________4____________ __________%%___$__7____8_

__,_ -___#__4______>_________________+_____ !(____.__7__)_8_____ /______________>____________________ _(___________'__7___$8___._ _________&_____&________!!!__&__E__5_________+__&__5 ______E__/__+___ ___ _______,_ ____%"__._$_7___'8___)_ _______2________


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_$)_ !__________________________ _(_______#____)_7___.8__'__ 2 _____-________@__N__F___#__!__&________'_________%____(____'__7____8__'$__ _____#_______@__F_________&________________________ _$___&%___.))_7____8__'$__ _____________>__E__-__________


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R2N, R2Pbase$_%,__ _______________________ ____ !_____ "_+________ 8 _77_ 9___.:+%;(-!_$ 7.)


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+ R2CH2NO2R2= H+ Nu H+R2= HNu= RO, RS, RNH,carbanions

Nef(Chapter 6)(Chapter 6)(Chapter 6) (Chapter 7)S)hee 9/

OH CO2MeS CO2MeHO O NO2SHN NHO

H HCO2HH+ CH3NO2+ HSCH2CO2Hd-biotin$_0,4.1 ADDITION TO NITROALKENES/

_-_________ ___ __ _____ __ ____ _____ __ _______________________#____ _________________ _ ________ ___#__ _ _$_08___$_5__________________ ___ __________________#____ _______________________ ___ ________ '_ ________ _"__ _____;_______ ______

__!

__ ___ _______; _______ __________ ____ ____ __________________________ ___+'_$_8,_7__ ______ _______________________________ _______ ___ __ __,________ _____ _

__+'_$_ ,_


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2) Pd/C, H23) COCl281%1) Zn/Ag, (CF3CO)2O+80%S)hee 91

O2NOAcO2N+ PhSH SPhX100%THFEt3N$_5,OO2N MeMeHSEt3N

OMeMeS NO2PhNCOEt3NS ONMeOMeH99%+82% ( 71/29)THF$_$,AcSNO2EtONaO2NSPh N C OEt3NS

NOLiAlH4SH2NHOSH2N HN CO


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3) Beckmann 2) COCl2rearrangement1) OH1) DMSO, Ac2O2) NH2OHbiotinS)hee 93

1 MICHAEL ADDITION_________ _ ____ ______________ _____ _____ __ _ __ _= ________%1__ _ __________________ __________________ ____ _ _______________ _________________________

_______ _ __ _____ __ +'_ $_!_ > _____ _ ____ ____________ ___ __________ _ _______ ___ _____ ________ _!_._______________ ______ _______ _ ________ __ _ __________ ______________ ________________!7____ _________________ _+'_$_7,_%%________ ___ ____

"_ __ _____ __ _________ ____________ _ ___ _+'_$_


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NO2MeMeMeMeMeSPh SPh

NO2NO2+PhSLi,J78 P, AcOH71

Q? (%) anti/syn88 40/6091/9PhSH, Et3N,BI+B*C * $_7,NO2NO2OHSPh88%TMG

+ PhSH + HCHOTMG: tetramethylguanidine$_8,4.1 ADDITION TO NITROALKENES3+_______ _ ____ _____ ____ ______________ ______ _____ _____ ____________ ___"_______ ___________________ _ _+'_$_%%,___ ___________ ___ ____%__0_,___________ __ _______-_&_ ________________ _ ___!7______________ _

__ _ ________ 4


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OCH2PhNO2EtOH, HClMePhOHNH2PhCH2ONaJ78 P 72% (syn/anti = 91/9)73% (syn/anti = 91/9)Pd/C, H2$_%1,+OHHNOHPhMeMe

NO2MeOPhNHCHONO2MeMeNHBocOH OR OH1) NaH,J78 P2) AcOH66% ( 94%)1) NaBH4, Pd/C Na/ NH32) Boc2OJ78 P80% (NO2NHBoc)75% ( 96%)$_%%,OH KH, THFPhNO2OPhNO22) 1 N-HCl1)RT80%

$_%0,OH NaH, THF NO2ONO294%RT1)2) 1 N-HCl$_%5,9 MICHAEL ADDITION__ _____ _ __________"__ ______ _____ _ _____ ___ ____ '_ _______;_______


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_____________ ______ _____________ ____ __ __ __ ________________ ______________)__ "____ _5_______0_______ _ __ ____________________

_____ __ ___ _____ _ ________________ ___________ ___ _____________

_ _+'_$_%$,_%7___ _ ______ ____ _____ ______ __ __ __ _ __ _ __________________________ __

_ __"___ ___ ____ __ ___ ___ _ 0____________ _ 5_______0_______ _ __ 81__ ___%7_#__ 5_______0_______ _ _ _______ ___ __ _______ _ ____ ________ _ _

______ ________ ______________________%

__________________;____________ ____ ___ ____________ _________ _ ______$-)_____ __ ________ _ ________ _____ __ __ __ _____ _;__ __ ____ __ ___ __ _ _;__ __ _ _ _"__

____2_ ___ _______,______ ____ ____ _____ ____"__ ___________ _+'_$_5 ,_$$MeOCHOPhSNO2MeO

1) Zn/HClMeO82%NHCHO2) HOCOCOCF33) NaIO4CH3NO2, PhSHEt3N53%$_5$,NO2XRNO2

XRNuO3OXRNuN , CH(CO2Me)2OONO2XR

t-BuOOLi NO2XRO

XRONuNu = OMe,Nu60J80%NuX = O, SS)hee 99


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?8 MICHAEL ADDITION#_ _ _________ ___________ _ ___ _____________________"_____ _______

__________________,____________________,_______________ __ ____ ______ _ __ ____

_+'_$_5!,_$8__ _ ___ ______________ ____ __ _ _______

_ __ ___________________>______ _____ ____;___________ ___ ______"_ ____ __ ____________ _____"_ __ _______ _ __ _ _______#__ _ $_8,_ $________________

____ __ _ __ _ ________ '___ _ ___ __ _____ ________ ________ _ __ ____ _____ ____ __ _ ____ _____ 8__,__ _ ___ _____________ _ ________&__ _ ____________ _____ _______ ___ _____________#__ _ $_8____________ __ ________ _ ___ __________ ____________________________ ___8_,__

_ ___ ______+'_$_57,_$!______ _ __ _ ____ _______________ _____ _____ ____________________ __$7NO

OSiNO2OCH2Ph NOOCO2CH2PhNOOSiNO2SPh N

OOCOSPhBu4NF, O364%THF52%1) Bu4NF, THF, O32) DBU$_58,$_5 ,O OMeO2N SPhHO ONKOOO OMeCOSPhHO O


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NOO80% (ds 15:1)2) O31)

$_57,NOSSiNO2OCH2Ph NSOCO2CH2PhHOHONSOCO2H H3N1) CF3SO2Cl80%2) LiN33) H2, Pd/CTHFSiBu4NF, O3

$_5!,4.1 ADDITION TO NITROALKENES?/>____ _ __ _ ____ ________ _________ _ __ ___ ____E,_______________________;___________ ______"____________________ _______ _+'_$_5


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HCOSPhHOOHO OHNH

CO2H3N NHOOOH

1) PhSCH2NO2,t-BuOK1) KOTMS, DMF,0 P94% (ds 50:1)2) MsCl,i-Pr2NEtO2N HPhSOOMeO

O2) O3, MeOH,J78 P83%OTMSS)hee 9;

SO2NiPr2SNO2NKOO

SO2NiPr2SONOO(R)

1)2) O3, J40 P61% ( 71%) $_5


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______"__________________________,______"____ __>_(__________ _ ____ ____ ___ ______ __ _______

_____ ________ %__________%_________ _ ______ ____ ____ ________ _ __

_ ____ _____ _____________"___________#__ _ $_ ,___ _ ___ _____ _ __ _ ____

____ _______ __"____

_______ %__________%_________ _ ___________ __"__ ___ _ _ ____ ____________________

__ _____ _ __"________ __ ___8%__ _________;______%_________ _ ________ _____ ___________ _________ _____________ _______ ________ _______________;___ %_5________ _______ 0, __ __"_______ _ __ __ ___ __

_ ___ __________ ____ ________"__ _____ ___ _=_,_______ _________ _

________ __"_____________ ___ __ ____ _ _______ ___ ____ _ ____ _____ _____ _ _____ __ __ _ _________ __"_______#__ _ $_!,_ 80+"_ _____ _ ____ _____ __ ____ _ _____ _ _ _ ____ ____ __ _ >____ ____

___ =_________ ____ _________ __ ___________ ___ _ __ _ ____

__"____________ _ ___ _#__ _ $_7,_85__ __ _ __ _ ____ _____ ______________________"______ _______ __________ _______

__"________%___________%_________ _ _____ __ ____ _+'_$_$%,_8$NO2O STolOt-BuOOLiPh3COOKNO2O STol

ONO2O STolOOONH3NH3STolO OOSTolO OONH2NH2J78 Panti 15:1J78Psyn 12:1S)hee 9


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TolSO Lit-BuOHOO2N OTolSsyn anti

Ph3COO KS)hee 9

Ph NO2NH STolO

t-BuOPh NO2NH STolO

t-BuO OHN OO

Ph COSTolLiOOButJ78 P43%$_$%,4.1 ADDITION TO NITROALKENES?3

_ _ _________ ____8__ __7_,_ _______"_ ____,_0______"__ ____,_ ___5_____

__"____________ ___________ _____ _____ _____ _____ _____ ____________-_ ______#__ _ $_


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STolO OSiNH282% ( 20:1) 65%86%S)hee 9?

NHOC(O)PhOOMeSiNO2KSKSNHSOOMeSiSMeNO2Cl CO2PNBONSOOMeSiSMeNO2

CO2PNBNS SMeNO2OSiMeO1)NS OCONH2CO2MeO

OHMe2) Me2SO476%1)2) P(OMe)31) 75%, 2) 90%LiN(SiMe3)260%S)hee 9=

?9 MICHAEL ADDITION


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9/3 Con0+(te A%%ition o' C(r-on4Centere% N0)leo2hiles9/3( A)ti.e Meth6lene Co2o0n%s -_______ _ _ __ ___ ___ _____ _ ___

_____________ __ _____________ ___ E____-&0___E___.,@_______________ _ ________________ _ _____________ __ _ _____ _____ ____ _ ______

____ ____________ _______ ____________________________ _____ _________ ___________ _______________ _ _______

____%_5____ ___ __8__ _____ __________________; _____________ __ _________@.___ ___,_ ___________ ___ ________ _)__

"____ _ __ _ ______ _ __ ___ __ ___ __ ____ __ ___ ____ _________ _ ____ __ __ __

__ _ __ ___!7__ ____ __ ____ _____ __________________ __ _____ __ ____ _____

__ ______________________ __8!_ ________ "_______________-_____,0__ ____ ____ _________ _____ ____________ _____ ___ ___________ _ _87O__________________ _____

________ __ _________ ______ _______; _________ _%_5____________________ __ ________ _ __ _______ ____________$_$$,__ _ _______________ _______________8 7% 8=> !0 8=> 0 !%=> 8! 8=> 78 !5=> !$Ph MeOONCH2PhOBuOOMeMeOOPhO2SO

OEtSPhCO2EtPh NPhCO2EtNO2NO2NO2NO2NO2NO2NO2

NO2MePhPhOONO2NO2NCH2Ph


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O2N OBuONO2OMeNO2MeOOPhO2S MeNO2OOEtNO2SPhCO2EtPh NO2N CO2EtPhPhPhS CO2H

NO2CO2HO SPh1) LDA, THF,J78 PSO2Ph2)3) H+80%EtNO21) LDA2)3) H+O

4) DBU82% (E/Z = 2/1)$_80,$_85,?? MICHAEL ADDITION_____ _____ ________________ ______ ,__________#__ _ $_%%___ ________ ___________ " _ _0___ __%_______%_____ _ _____ _____ -___ _______ ________ ___7____________________ _____________ ________ _____ ____________________ _________________________ _____________________(__ _ _______ ___

__ ____ _____ ___________$_8$___$_88,____ _ __ __

____________ _= ________+'_$_ $,_753__ _____________ _____ _____ _ "_ ____ ____ _ _______ __ _ __________ _____ ____________________ _______ ___

_________ ____ __ _____%_$____ ___ _____ - _ ______+'_$_ 8,_ 7$__ _ _______________________ _ ______ +'_$_ ,_78_=__ ____ __ _____ _ _ _______________ _

_______95E0:__________; __________78_OSiMe3NO2Me MeOO1) SnCl4+2) H+, H2O85%$_ 0,MeOSiMe3OMeNO2MeMe CO2Me


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OPhNO2MeNOOMeNO2Ph+MeCN1. RT2.~100%$_ ,ONPh NO2O

NNO2HPhONNO2HPh+ONNO2HPhON PhNO2ONNO2HPh++$_ !,NOMePhNO2NO2OHPh+Et2O, RT70% (de > 90%)


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$_ 7,ONMeMeNO2Ph

O ButONO2PhMe MeO+1) CH2Cl2,J78 P2) HCl59% ( >95%)$_


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Me HNO2MeOOMe

MeO+1) THF,0 P2) AcOH-H2O+77% (1 : 8)68% (95% )1) NaOH2) HCl$_!%,NMe

ButMe2SiOOPhNO2NOMeOPhNO2+SnCl4J78 P66% (90% )

$_!0,4.1 ADDITION TO NITROALKENES=;__ %_$____________ ____ __ _______________ ________ _"__ __"__ _______ _,________"___________

_ _________ _____________________#__ _ $_%$,_


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1) Et2O2) H+CeCl3THF78%++ MeMgBr

$_!5,$_!$,CONEt2NO2CONEt2O2NNHOHH2)1) sec-BuLiTMEDA,J78 P

79% 63%1) NaBH4, NiCl22) sec-BuLi$_!8,PhNO2Ph NPhH2COMgClOPhPhCH2NO2PhPhCH2N

ClOHPhPhCH2CO2HH+PhCH2MgBr85%H2SO4concn HCldil. HCl95%93%

53%S)hee 9/9

=< MICHAEL ADDITION_____ ____ ________%_$_________________ ________ ____ __________________________________ '_ __ ___________-.0___________ ______ __+'_$_!


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_-________ _ _ _____________;____ __ ________>_)_______ __ __________ __

__________________ "_ __ ____ __+'_$_71,_%10__ _ ____________ _____________ _ __ '___ ___ _________ _______ __+'_$_7%,_%15#_________ _ __ _______________ _ _____ __ _ __ _____ $_____

__ ______________

________+'_$_70,_%1$ArNO2ArNO2RArRR2Zn, MgBr220 PR2Zn20 P 99% ? 40% ?

S)hee 9/;+ THFT80%NO2ClC5H11ClPhNO2PhEtPhNO2+

Ni(acac)2, Et3NTHF90%PhEtEt3GaHexaneClNPhEt OH68%Ph +NO2Ph

Et+ Et3Al concn HCl +24% 49%C5H11ZnIEt3BRT$_! ,$_!7,$_!


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$_!!,PhNO2ZnBr PhNO2PhNO2SnBu3NO2MePh+ DMF83%+TiCl453% (anti/syn = 7/3)RTCH2Cl2$_71,$_7%,4.1 ADDITION TO NITROALKENES=____ __________ _____ _ _ ___ ___ _________ _ __ ___@___-,_(__________ _ ____ ______________; _;__________ _________

_ ___________ _____ _ __ __ ____ _ _ _______ _ __ __ ________ _ __ _&)_______ ____ _ _______- 0=____ __ _ ____ _ _ __ ___ ___ __ ________ _ _ __ ____ __ ____ _

_____ __ ________________; ___________ _+'_$_75,_%18________ ___ _______ ________ ____%_5_______ _____ __________ ______ __

_______________ ____________ __________ _ ________ '_ ___ _______+'_$_7$,_%1__ _____ _____________ _______ ___ _________ _ ____ ____ _________ __ _____

__ ______________ __ ________ _____ _______________ _________+'_$_78,_%1!@ ________

_______ _ ________ ___________________ _ _____ _ __ _______________+'_$_7 %17___+'_$_7!_%1


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NBocCu(CN)ZnClO2NO2N+J78 P

H2/PtO262% 80%NMeBocH2N NMeBocTHFRT$_7$,Br 2) CuCN, LiCl, THFOEtO

OONO2OO NO21) Zn, LiI, DME,75 PTHFCO2Et$_78,Cu(CN)ZnIPhNO2O2NJ78 P 0 P Ph+

78%DME$_7 ,=? MICHAEL ADDITION>______;_____ ___ ___ ________________ _ ______"___ __&)______

_________________ -_,_____ __ ________________________ __+'_$_77,_%%1.________________________ ____________ _____ ___%_$___________________ _ __________+'_$_7>._=__ _+'_$_>.=______ ___ _______ ___ "_ __

__________"______ __< _) ______________ _____ __ _____ _(,______________ __________________ ____________ ________ ________;____ __ ________________ ________ ___ ____

_ ____________"___ __ ___________ ________ ___ _______ _%_$___________________ "_ __ ____

_____________ +'_$_


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NO2AlEt2NO2+J15 P86% ( = 93/7)$_7


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(1.2 ?%)+ cat.(2.4 ?%)ONO2OEt2Zn64% (25% )Cu(OTf)2

(1.2 ?%)cat.(2.4 ?%)OOP N+Et2Zn95% (92% )cat.$_


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NO2MeMeLi77%THF$_


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OZnClOONO2Me+J78 P

THFRMeTrTBSYield (%)7582ee (%)92568388$_

OMeOOZnClEt OOEtNO2NO2EtEtJ78 P+89% (96% )THF$_< ,

N OSiMe2ButN OSiMe2ButNO2NHNH MeOHN PhPhOMe

1)n-BuLi NO22) ZnCl2

85% (95% )$_


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NO2MeONHONMeMeO+

84%1) n-BuLi2) ZnCl2$_


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2) ZnCl2MeJ78 P91% (84% )_ _!"!#OO

NO2NHNNHNHHNNOOONO2HO2C H

OHNMeNH MeOOMeHNOONO2OOH

HCO2HOMe(S)HHCO2H(S)(R)(B. 121)(B. 122)(B. 123)S)hee 9/


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O2NSO2PhO2NSO2Ph(CH2)3Cu(CN)ZnINO2NO2

HHPriCu(CN)ZnBrOAc O2NSO2PhPriOAcEt2OC(CH2)3INO2Zn, CuCN2 equiv LiClEtO2C(CH2)3Cu(CN)ZnIEtO2C(CH2)3CH=CHNO2THF, 60 P

SiO2hexane, RT85%THF, 60 P, 2 h74%81%(overall yield)_ _!"$#_ _!"4#_ _!" #NNO2OMeMeN

NO2OMeBr MeNNH2OMeMeNNHCO2EtOMeMeN NMeHMe MeBrN NMeHMe MeRO1) LiAlH42) NBSNaOMe, CuI R = MeR = CONHMe


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ClCO2EtBr2, ButOK 1) ButOK, DMSO2) H2, PtO275%29% (3 steps) 35%35%S)hee 9/

R1HR NO2R2YYR2RR1NO2+baseY = CO2Et, C(O)R3, CN, S(O)Ph, SO2Ph, etc.base = RO-, F-, R3N, R3P, tetramethylguanidine (TMG), DBU, etc.S)hee 9/?

4 . 3 M I C HAEL ADDITION OF NITROALKANES/83:_ _ _ ______ ____ __ ___ __ __ _ _ ___ _ _____ 3_ ___ ___

__ _____ ___ ___ _______ _ _______ _________ ______ _!"5#!4___ __ _____ _ ___________ __2___ _________3______ _____ _

________;#___ _ _ _______ __ _________ ____ _________

_____________ _______ _!"%#!45______________ __3_________ _____________________ ___ ______ _!"(#_!4%__6>______ ___ _____ ________ _6____ _____________________

_____________ ______ ____ __ ___ __ ___ _ __ _ _______ _____ __!1($_!4()!

"_9______ ____ _ ___ _ ___ __ ___ _____________ ___ _6____ _______________ ____ _____ ____ __! !__ __ _______________ _________ ______3_________ __ __

__3__ __ _3______ _3________ __ ___ ______, __ ____6>____ ___ _ __ _ 6____ __ _______ ___ ________ ______________

_____!"+#_! $_ ________________ _______ __ ____ ____ _______ __ __ _ _____ __ ____ _ ___ ______________ __6____ _____________________ ____ 3_____ _ _$#_! 4)! 58__ _ ___ ___3___ _ ______ ____ __ ___ _______________

________________ __ _______________ _ _______ _____ __ _ _____ ____ _____ ___ ____ __ _6____ __ ________ ___ _______________ ___________ __ _ ______ __ _____ ______29__"_"$5_6#________

___ _ _ ____ _______ ___________________ __._&._#_ ___ ________ __________ __ __ _ ___ _ _ _____________ ________ _!"1#_! %___ _6____ __________________ ___ _____ ____________

_________ _________ _________29_________ _______ ___ _________________ _ _$#_! (

Me HMe NO2SOPhO2N SOPhMe MeMe HMe NO2CO2MeMeO2N CO2Me


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Me MeMe+RT, 24 hMeCNbase (1.0 equiv)(2)

Base0Yield (%)TMGEt3N60DBU95MeCN+base (1.0 equiv)RT, 24 h0(3)Yield (%)DBU

Et3NTMGBase1961_ _!"%#_ _!"(#MeMeNO2CNCNMeNO2

+TMG (0.1 equiv)MeCN72%_ _!"+#Me HMe NO2MeOO2NMe MeMeO+

NaOH (0.025 M)CTACl, RT, 1 h_ _!"1#ONO2MeOOMeO


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NO2+PPh3THFRT, 24 h94%_ _!"5#/89 MICHAEL ADDITION

________ __ ______________________________________________ &__ _ -_3_$_____ _+4# !4(.94_.9$#_2$_6> _% # !41.94_2$_6> _((# ! "

_.94#$.9_2$


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OMe NNO2MeOC6H13Me

NO2OO2NMeO2CONO2MeMeMeCO2EtO2NPh NO2N SO CO2Me[NC(H2C)2]3

NO2NCMeF3C NO2MeONO2[NC(H2C)2]3NO2H3C NO2CF34 . 3 M I C HAEL ADDITION OF NITROALKANES/8;N__ _____________ ______ ___ _ ___ __ ____ ________________ _6____

___________________ __ __

___ _ ______ _______ _!!"#_! 1__ __ _ ___ __________________ ______ ____ ________ ___________ _____ _______

._ ______________________ ___ _ ___ ___________________________ __ __ _____ __ _3

____ ____________________3____ ___ __________


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_ ______ __ __________ _ _____(_$#__________ _____________________ __ ___ __________

Me CO2EtNO2MeO

O2NMe CO2EtMeO98%+Yb(OTf)3H2O, RT_ _!!"#Me HMe NO2MeOO2NMe MeMeOMe HMe NO2CO2MePhO2N CO2MeMe MePh75%+Amberlyst A-21Solvent FreeRT, 25 h

+K2CO3Aliquat 336)))), 90 h70%_ _!!!#_ _!!$#ONO2NO2OMeNMe

+HMS, RT, 2.5 h93%Si(OMe)3_ _!!4#O2N CO2MeMe Me NHCbzH CO2MeMe Me NHCbzBu3SnH


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AIBN67%_ _!!5#O2N HMe MeNHCbzCO2Me

O2N CO2Me+ Me Me NHCbzBu4NFRT, 22 h85%_ _!! #/8< MICHAEL ADDITION_!!5#_!54_.__ _______________________3_________ _3_______ ________ _________

__ _______________________________ _!!%#_!5___ ____ _______, __ _ ______________ ___ _ ________________ _______ ___ __ __ _______________________ _!!(O___ ______ _________________ __ ________________________________________________ __ ___ ___________62_!55__ _6____ _____________________ _____3_________ ___ __ _______ _______ __

___ __________ _ __ ___ _____ ________ ___________ _________________________________ _ ____

_____ %_!3_ ____ ____ __#__ _____ _____ ___ ___ _ _ ___ __ _ _ ___ _ __________ __ _ __ ________ __!3 ____________________!5%_)__7__________________________ __ ___ ___ _______________

_!5(________ 3_______ ______ ___ ________ ______________ _________3____________ _ _ _!1_!5%_

OHC CO2HO2N HMe Me O2NCO2-

NH3+

Me Me+ NH3+50%KOH-H2O_ _!!%#Ph NHPhO SO2PhPh NHPhO

NO2Ph NHPhO CO2H88%NaH-CH3NO2THF, RT, 1 h90%KMnO4_ _!!(#


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CHOHO OH NO2OOONO2O

O OOOO OCHOOOOO+CH3NO2O1) Bu3P2) H+,

62% 95%85%H2O2K2CO3H+Ph3P=CHCH2CH390%60% 83%TMGOHOCO2MeOCO2MeNO2OCO2MeCHOO(Nef) Wittig CO2MeOCH3NO2CH2NO2CHOTMG70%1. NaOMe, MeOH2. H2SO471%S)hee 918S)hee 9/=

4 . 3 M I C HAEL ADDITION OF NITROALKANES/8__ _6____ __________________ ___ __________ _ _ __ _______ _______

__________ ___________________ ___ _ _ _$"#_!5+_9 _ 3_ __ _____________ ___ _______________________

______


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_ ________________________________ _____________ ____ _______ _ _ _$$#_!%"__ _6____ ______________________________ _ ______ ____ ______ ________________________________________ ___3___________


150/497

1) NaOH, EtOH58%2) H2SO4, n-hexane,H2O, 0 C,1 h(2S, 5R, 7S) (2S, 5S, 7S)(Z, Z) (E, E)41% (1:3)+

S)hee 911/8? MICHAEL ADDITION._____ ____________________ ___________


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OOAcOMeOAc ONO2OAcO OOMeOH OAc2O, py, RT98%KF, Bu4NBr,15% TiCl3, pH 5.3O Omethyl propiolateDMSO62%60%O OOOOO

95%HO(CH2)2OHp-TsOH95%KOHMeOH()-(R, R)-PyrenophorinES)hee 913

Me3SiOCO2Me+ NO2Triton B

CO2MeO

NO280%_ _!$"#4 . 3 M I C HAEL ADDITION OF NITROALKANES/8=OHOOHOOHOO2NOOOO

OOH2NNHONHOORO O OO


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OOOOOOHNOOOOO OOOOHOOHOOHOO2N NHONH

OOO O OOOOOOOOHNOOOO

O OOOHNONHOOOOOOO O OO OO

NHOOOOOOOONHO


153/497

HNO OOOOOOOO OH2, Raney NiR = NO2R = NH2OO+HNO ODCC: dicyclohexylcarbodiimideHOBT: 1-hydroxybenzotriazoleDCC, HOBTO ODMF3

OOR = NO2R = NH2H2, Raney NiOODMFDCC, HOBTOHNONHHNO

RS)hee 919

NO2PhEtNO2NHPhH2C1) n-BuLi, THF, 78 P2) PhCH2N=CHPh3) THF, AcOH, 78 0 P95% (anti/syn = 10/1)_ _!$!#//8 MICHAEL ADDITION__ __ __ _ ____ __ _6____ _____________________ ______ ______________ _____

____ _____ ____ ______ _ ___________________ ___ _ _______ ______ _______ ___ _

_____ _ ____ ____ _______ _!$$#_!%+O O2NMeOCO2MeMeO


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O2NCO2MeSO2PhMeOO2NPhO2S CO2MeMeOHPhO2S CO2Me80 PBu3SnHDBU benzeneMeNO2AIBN_ _!$$#CHOMeTBDMSO

MeMeTBDMSOMeNO2MeROMeNO2O OTBDMSMeOMeNO2OO OTBDMSMeMeOMe62%OO OTBDMS1) MeONa, MeNO2,MeOH, RT, 2 hMe2) MsCl, Et3N, CH2Cl2

0 P, 1 hMeOMe2) CH3CN/H2O, HF,RT, 24 hO1) NaBH4, CHCl3/i-PrOH,RT, 40 min amberlyst A-21, Et2O,RT, 2 h


155/497

Me70%OO3) (S)-2-methylbutyricanhydride, DMAP,40 P, 20 min59%

HO55%(+)-dihydromevinolinn-Bu3SnH, AIBNtoluenereflux, 30 minS)hee 91;

4 . 3 M I C HAEL ADDITION OF NITROALKANES///9_ _____________ ______ ___ ____________ ___________________ ________#_________

__________ _ _ _$5#_!%1


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_ _!$4#Me MeO OMeMeOOH CH2PhMeMeOOH CH2PhNCH2PhMe MePh+ PhCH2CH2NO2DBUMeCN

77%Pd/CH295%PhCH2NH292%_ _!$ #H2C)nONO2CHO(H2C)nO

CHO(H2C)nOONO2(H2C)nOOHn = 0, 1, 2, 6nPPh384J93%75J81%

NaHDME90J95%NaBH4NO2NO2_ _!$5#//1 MICHAEL ADDITION

__ _6____ __________ __________ __ __ ___3_________ ___ __ __ _________________


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_ ______________ ______ _________ _________ ___ ___________!3 ____ ____!4 __!__ ___ ___ _

!35____ 3_______ _________ __ ___ ___ ______________ _3______ ___ _______________ _______

_!$(#_!(__ _6____ ______________________________3_________ ___ __ _____ __ ________

____

_ ____________ _________________________ __________ ___ _____________________ ______ ____________ _ _ ____.____ __!"_____ ________ ________#_931 Intr(ole)0l(r A%%ition8______ ______6____ _______________________________ _________ _ __ _

____ _____________________ _____________________________________ _ __ _ ___________ _6____

____________!___ _________ _ _ ___ ________ _ _____ __ ___ __ ___ __ ____6 2___ __ 6 29_ ___ _ ______4___ ___ ____ ____________ _ __ _ _____________ _!$+#_ !(5OPhNO2

O PhNO2OHHPhNO2OHHPhNO21) LDA2)75%MeONa-MeOH +45% (7:93)RT_ _!$+#PhONO2OPhO ONO2PhO O

PPh3

71%+AIBNBu3SnH70%_ _!$(#ONO2O O


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NO2ONO2O Me O MePPh3(S)-alpine

hydride72%Bu3SnH44%AIBN_ _!$%#4 . 3 M I C HAEL ADDITION OF NITROALKANES//3;____ _6____ _____________________________ ______ __ _ ___________________4______$__ ___ ____9______________ ___________ __ _____________ _ __ _

___________ ____________________ ______ _______ __________________________ _;_______ __________ ___

________ _______ _!$1#_!(%__ _ _______ ______6____ __ ________ ___ __ __ ___ __ _ __ __ __ ____ ____

____ ___ ___________ _ _ _$%#_!((__________ ____

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