2 ,

3. 4. 5.

H. J. Mark , J. Am. Chem. Sot . , 81, 3188 (1959). R. W. Hag and L. F. Hook, Aust ra l . J. Chem., 17, 601 (1964). Yu. I. Pe t rov , Dis se r t a t ion , Moscow (1966).

E. I. Klabunovsldi and A. A. Vedenyapin, A s y m m e t r i c Ca ta lys i s , Hydrogenation on Metals [in Russian] , Nauka, Moscow (1980), pp. 75, 82.

O X I D A T I V E A D D I T I O N O F A C E T O N E TO B U T A D I E N E

M. G. V i n o g r a d o v , M. S. P o g o s y a n , UDC 542.943+542.955:547.284.3:547.315.2 A. Y a . S h t e i n s h n e i d e r , a n d G. I . N i k i s h i n

The oxidative addition of acety lacetone and o ther 1, 3-d icarbonyl compounds to conjugated dienes in the p r e s e n c e of the s y s t e m Mn(OAc)3-Cu(OAc) 2 r e su l t s in the se lec t ive fo rmat ion of 5-vinyl -4 , 5-dihydrofurans [1]. There a r e , however , no r e p o r t s in the l i t e r a tu r e on the oxidative addition of monocarbonyl compounds to diene s.

We have found that acetone r e a c t s with butadiene at 80~ in ace t ic acid containing Mn(OAc)3 to f o r m 5- ace toxy -6 -hep t en -2 -one (Ia), t h ree i s o m e r i c 1 -methy l -3 , 7-divinyl-2 , 8 -d ioxa-c i s -b ieyc lo[3 .3 .0]oe tanes (II)-(IV), and t h r ee d i a s t e r e o i s o m e r i c 1 ,6-dioxaspiro[4.

oAc

0 0" " "0

Me

CIa) (u)

(v)

nonanes (V)- (VII).

H

Me Me

(hi) (IV)

(w) (vn)

The s t r u c t u r e s of the p roduc t s were conf i rmed by PMR spec t roscopy with the shift reagent europium t r i s - (1 , 1, 1, 2 , 2 , 3 , 3 - h e p t a f l u o r o - 7, 7 -d ime thy l -4 ,6 -oc tad iona te ) , double homonuclear 13C NMR resonance spec t roscopy , and IR and m a s s spec t roscopy .

The fo rmat ion of the b icycl ic p roduc t s (II)-(VII) is favored by the use of Cu(OAc) 2 as catalyst . The p r o - por t ions of the ke toes t e r (Ia) and the b icycl ic compounds (II)-(VII) a re also dependent on the acetone:Mn(OAc)3 ra t io (see Table 1). When this ra t io is d e c r e a s e d f r o m 10 to 2, the amounts of the compounds (II)-(VII) in- c r e a s e f r o m 32 to 82~c, but the ove ra l l y ie lds of (Ia)-(VII) dec rea se . The ra t ios of the total condensed (II)-(IV) and sp i ro -compounds (V)-(VII) a re 3:1, and a r e unaffected by the exper imenta l conditions.

The spat ial or ienta t ion of the vinyl groups in the i s o m e r i c dioxabicyclooctanes (II)-(IV) is shown by the e f fec ts of the shift reagent on the chemical shifts of the CH and CH 3 pro tons in these i s o m e r s . F o r all three i s o m e r s (II)-(IV), the s ignals fo r the CH and CH 3 pro tons in the PMR spec t rum were shifted downfield to a much g r e a t e r extent than the signals for the p ro tons of the o ther groups. This shows that the sMft reager~t coordinates p r e f e r en t i a l l y with the oxygen a toms of the t e t r ahydro fu ran r ings .

Study of spat ia l mode ls of the dioxabicyclooetanes (II)-(IV) shows that the approach of the sMft reagent to the oxygen a toms is g rea t ly h indered in the endo, endo i s o m e r (IV). In the exo, endo i s o m e r (III), the oxygen a toms a re s c r eened by one vinyl group, and in the exo, exo i s o m e r (II), by two vinyl groups.

In the ca se s of i s o m e r s (II)-(IV), the shifts in the PMR signals fo r the CH and CH 3 groups to lower field on addition of the shift reagent i nc rea se in the sequence: (II) < ( I I I ) < (IV). F o r ins tance , the PMR signals of the CH 3 groups in these i s o m e r s a re shifted downfield by 0.12, 0.36, and 1.04 ppm, respec t ive ly . Consequently, compound (IV), which f o r m s a complex with the shift reagelI t m o r e readi ly than the o the r i s o m e r s , can be a s - signed the endo, endo configurat ion, and compound (I I ) the exo, exo configuration. The ra t io of the s t e r e o i s o -

mers was (II):(III):(IV) = 1:1:2 (GLC).

.......... N. D.--Zel~ns-ki=l-Instituteof Org~ani--c-Chemistry, Aca-delny of--S-ciene-esof-t-f~e-(.lSSR,-Mose--ow. Trans la ted f r o m Izves t iya Akademii Nauk SSSR, Ser iya Khimicheskaya , No. 4, pp. 842-847, Apri l , 1983. Original a r t ic le

submit ted June 18, 1982.

768 0568- 523 0 / 83/32 04- 0768 $ 07.50 �9 19 83 Plenum Publishing Corpora t ion

TABLE 1. Effect of the Acetone: Mn(III) Ratio on the Composi t ion of the P roduc t s of the React ion of Acetone with Butadiene*

Acetone: [ (II)--(VlI) ]: Overall Mn(III) : (Ia) yield, %t"

l0 5 2

0,t5 l 23 0,45 45 t,5 2 8 4,6 20

'0.117 mole of butadiene, 0.1 mole of Mn(OAc)3.2H20, 0.001 mole of Cu(OAc)2.H20, a n d l 0 0 m l o f A c O H .

Calculated on the consumption of 2 moles of Mn(III) for the fo rmat ion of (ia), and 4 moles for the f o r m a - tion of (II)-{VII).

In the absence of copper aceta te .

The i s o m e r i c d ioxaspi rononanes (V)-(VII) were fo rmed in a rgt io of 3:3:1, but the spec t ra l data obtained were insufficient to allow the spat ia l s t r u c t u r e s of these i s o m e r s to be es tabl ished.

The fo rmat ion of (Ia)-(VII) may be r e p r e s e n t e d by the following scheme:

,~,,x, F -1 V ~ 'q F .~-. ~ - I -.. / ~ / / 2 / + ~ t K v...-~.~ I +,,,~ k . . .~c7 -.-- ~ ,~o,,,.

o ~ ~ - % o ~ ~ ~ ~ ~ _ L U. LSv,,,, J

(x)

(xI) (xiv)

F ~ r- o~,~,,~ -"!

(xm) (xvi)

(II)- (Iv) ( v ) - (vii)

X=OAc; R=Ac(a), H(b), The pr inc ipa l d i f ference between this scheme and that p roposed p rev ious ly for the reac t ion of ace ty l -

acetone with conjugated dienes [1] is the fo rma t ion of a complex of Mn(III) with the in te rmedia te ketoalcohoI

769

(X), which is the product of the oxide~tive addition of acetone to butadiene. The l a t t e r is conver ted into the chelated hydroxyallyl complexes (XI) and (:(IV), which then reac t with a second molecule of butadiene. Oxida- tion of the in termedia te allyl radicals (VIII), (XII), and (XV) proceeds regiose lee t ive ly at the nonterminal atom of the allyl sys tem with the format ion of compounds (Ia), (II)-(IV), and (V)-(VII), r espec t ive ly , probably as a resu l t of ir~tramolecular stabil ization of the carbonium ion in termedia tes (IX), (XIII), and (XVI) by the carbonyl group [2].

In o r d e r to conf i rm the proposed mechanism, we studied the oxidative addition of acetopropyl alcohol and dihydrosylvan to btEadiene in the p r e sence of the oxidative sys tem Mn(OAc) 3-Cu(OAc) 2, which models the fo r - mation of the final p roduc ts (II)-(VII) f rom the ketoalcohol (Ib). There were obtained the condensed (XVII), (XVIII) and spiran compounds (X/X), (XX), which a re analogous in s t ruc ture to compounds (II)-(IV) and (V)- (VII), r e spec t ive ly , but contain a single vinyl substituent. As a resul t of this , they are r ep resen ted in each case by only two i somers . Since the react ion takes place in AeOH, there is also observed par t ia l conversion of acetopropyl alcohol and dihydrosylvan irate y-ace topropyl acetate:

O

or -4- Me hre

(XVII) (XVHI) o. .o.. ~t

(xlx) (xx)

Compound (XVII) is assigned the s t ruc tu re with an exo-posi t ion and compound (XVIII) that with an endo- posi t ion, of the vinyl group, since the i r PMR spec t ra a re s imi la r to those of the exo, exo and endo, endo-di- vinyl-subst i tuted dioxabicyclooctanes (II) and (IV).

The quantitative composit ion of the products (XVII)-(XX) and the overal l yields (70%) were the same for the reac t ions of butadiene with acetopropyl alcohol and dihydrosylvan. The (XVIII):(XVII) ra t io was 1.7. The rat io of the s p i r o - d i a s t e r e o i s o m e r s was 1.5, but as in the case of the divinyldioxaspirononanes (V)-(VII), the spect ra l data were inadequate to de te rmine whether i so m er (XIX) o r (XX) predominated. The ratio [(XVII) +

(XVIII)]:[(XIX) +(XX)] = 5:3.

The identical yields and product composit ions in the react ions of acetopropyl alcohol and dihydrosylvan with butadiene indicates that there is an equil ibr ium in the acet ic acid solution between acetopropyl alcohol (R = H), its acetate (R= Ac), and dihydrosylvan, as a resuR of which in both cases it is evident that the same s ta t ionary concentrat ions of the in termediate complex of Mn(III) with the ketoalcohol are established:

OR 1~+ [ r .

Mn(tH) ~' nOH �9 ,] "~TI'/~I/Ro 0 - - A \ / / ] R'= vinyl*(II)-(VII,

",~ / [ ~" =___________~ ,(xviI)-(xx) Mn(III) _]

R : H , Ac.

The ability of acetopropyl alcohol and dihydrosylvan to undergo facile in te rconvers ion in acidic media

has been repor ted prev ious ly [3].

In the cases of the ketoalcohoI (Ib) and the ke toes te r (Ia), this equil ibrium should obviously be established even more readi ly as a resu l t of the g r e a t e r stabili ty of the carbonium ion intermediate in which R' : vinyl (IX). It was in fact shown in a control exper iment that the ke toes te r (Ia) was readi ly converted under the react ion con-

ditions into (II)- (VII).

It is noteworthy that the acetyI group in the 3 position of the 4, 5-dihydrofuran ring confers stabili ty to- ward solvoiysis in glacial or aqueous AcOH. Consequently, the 4, 5-dihydrofuran is the main product of the

oxidative addition of acetyiacetone to butadiene [1].

770

EXPERIMENTAL

~3C NMR and IH NMR spectra were obtained in CDCI 3 in a Brucker WM-250 spectrometer, internal stan- dard TMS, and IR spectra as microlayers in a Specord UV-VIS spectrometer, in CCI 4. GLC was carried out with an LKhM-8MD/5 instrument with a flame-ionization detector, on a steel column (No. i) 300 x 0.3 cm, 5%

XE-60 on Chromatone N-AW (0.2-0.25 ram), and on a glass capillary column (No.2), 5000 x0.026 era, PEG-40M, carrier gas nitrogen.

Europium iris(l, i, i, 2,2,3, 3-heptafluoro-7, 7-dimethy[-4,6-octadtonate) (produced by the Perm Insti- tute of Pharmacy) was used as the shift reagent without further purification. Mn(III) acetate was obtained as described in [4]. The Mn(III) content, by eerimetry, was 19.1% (calculated, 20.5%). Acetone, acetic acid (cp grade), and butadiene (93.2% purity) were used without further purification. Dihydrosylvan was obtained by dehydration of acetopropyl alcohol [3].

Reaction of Acetone with Butadiene. A mixture of 232 g (4 moles) of acetone, 25.2 g (0.47 mole) of buta- diene, 107.2 g (0.4 mole) of Mn(OAc)3 �9 2H20 , 0.8 g (0.004 mole) of Cu(OAc) 2 �9 H20 , and 400 ml of AeOH was stirred for 3 h at 80~ in an autoclave. The reaction mixture, containing the ketoester (Ia), the isomeric dioxabicycio- octanes (II)-(IV), and the dioxaspirononanes (V)-(VII) was analyzed by GLC and TLC (L40/100 silica gel, sol- vent hexane:ether, 4:1). The Rf values were: 0.18 (Ia), 0.39 (If), 0.42 (III), 0.47 (IV), 0.63 (V), 0.66 (Vl), 0.70 (VII). The retention times on column 2 (carrier gas rate 0.35 ml/min, bp 130~ for compounds (la)-(VII) (rain) were: 20 (Ia), 13.4 (II) and (Ill), 14.2 (IV), 7.62 (V), 7.2 (VI), 7 (VII).

The reaction products were isolated by pouring the mixture into water and extracting with ether. The ether extract was washed with water, dried over MgSO4, excess starting materials distilled off, and the resi- due distilled in vacuo. There were isolated 2.5 g of 5-acetoxy-6-hepten-2-one (la), bp 120-122~ (30 ram), and 3 g of a mixture of (II)-(VII), bp I05-120~ (30 ram).

Products (II)-(VII) were separated by adsorption chromatography (silical gel L40/100, solvent hexane- ether). Elution was effected by gradually reducing the hexane:ether ratio from 16:1 to 4:1. There were thus obtained: pure endo, endo-(IV), a fraction containing a mixture of exo, exo- and exo,endo-(II) and (III), and a fraction containing a mixture of the diastereoisomers (V)-(VII).

o

5-Aeetoxy-6-hepten-2-one (la). Found: C 63.13; H 8.10%. CgHI403. Calculated: C 63.53; H 8.24%. IR- spectrum (v, cm-i): 995 (=CH), 1650 (C =C), 1720 (C=O), 1740 (OC =O). PMR spectrum (5, ppm): 1.97 s and 2.05 s (2CH3CO), 2.39 t (CH2CO,J = 7 Hz), 5.0-5.3 m (=CH2, HCO), 5.53-5.93 m (=CH, 7 lines).

l~,Methyl-3, 7-divinyl-2,8-_di_gxa-cis-bic cxpJoj~3.3.0]pctanes (II)-(IV). Found: C 72.80; H 8.73%. CiiHi602. Calculated: C 73.33; H 8.88%. IR spectrum of the mixture of (II)-(IV) (u, era-i): 995 (=CH), 1650 (C =C), 3090 (=CH).

e x o , e x o - I s o m e r (II). PMR s pec t rum ((, ppm): 1.51 s (CH3), 1.69-1.76 m and 2.24-2.38 m (2CH2), 2.54- 2.63 m (CH), 4.49-4.58 m (2CHO), 5.11. d.q (CHart b =, J = 10 and 1.5 Hz), 5.27 d.q (CHart b =, J = 17 and 1.5 Hz), 5.91-6.06 m (2CH =, 7 l ines) .

e x o , e n d o - I s o m e r (III). PMR s pec t rum (5, ppm): 1.52 s (CH3), 1.77-1.83 m and 2.28-2.39 m (2CH2) , 2.57- 2.64 m (CH), 4.22-4.31 m and 4.49-4.58 m (2CHO), 5.15 d.q (CH_aHb =, J = 10 and 1.5 Hz), 5.30 d.q (CHaH b =, J = 17 and 1.5 Hz), 5.79-5.92 and 5.88-5.96 m (2CH, 14 lines).

endo~endo- I somer (IV). PMR s pec t rum (5, ppm): 1.57 s (CH~), 1.93-2.00 m (2CH2), 2.68 quint. (CH, J = 6Hz) , 4 .64q(2CHO, J = 8 Hz), 5.12 d.d.d (CHaHb = , J -~ 10, 1.5, and 1 Hz), 5.28 d.d.d (CHa_Hb = , J = 17, 1.5, and 1 Hz), 5.73-5.87 m (2 CH = , 7 l ines) . Mass spec t rum (m/z) : 180 (M+).

(2S*, 5S*, 7S*-, 2S*, 5S*, 7R*- , and 2R*, 5S*, 7R*-) 2, 7 -d iv iny l - l ,6 -d ioxasp i ro [4 .4 ]nonanes (V)-(VII), Found: C 72.90; H 8.75%. CllH1GO 2. Calculated: C 73.33; H 8.88%. IR spec t rum (u, cm-1): 1645 (C =C) , 3090 (CH =). PMR spec t rum of the mix tu re of i s o m e r s (V)-(VII): (6, ppm): 1.85-2.36 m (4CHz), 4.35-4.65 m (2CHO), 5.07-5.28 m (2CH2=), 5.78-6.03 (complex mul t ip le t cor responding to =CH). The spec t rum was in accordance with that of 2 , 8 - d i m e t h y l - 1 , 6-dioxaspiro[4.4]nonane [5].

React ion of Acetopropyl Alcohol and Dihydrosylvan with Butadiene. A mix tu re of 10.2 g (0.1 mole) of ace topropyl alcohol or 8.4 g (0.1 mole) of d ihydrosylvan, 5.4 g (0.1 mole) of butadiene, 26.8 g (0.1 mole) of Mn(OAc)3.2H20, 0.2 g (0.001 mole) of Cu(OAc)2.H20, and 100 ml of AcOH was shaken for 3 h in a meta l ampule at 80~ According to GLC, the overa l l yield of (XVII-(XX) calculated on Mn(III) ace ta te was 68%. To isolate the p roduc t s , the mix tu re was poured into wa te r and ex t rac ted with e ther . The ex t rac t was washed with water ,

77l

dried o v e r MgSO4, excess s ta r t ing m a t e r i a l s dis t i l led off, and the res idue dist i l led in vacuo. The re were ob- tained 1.03 g of T-aee topropyi ace ta te , bp l l ( ?C (30 ram) and 5.3 g of a mix tu re of (XVII)-(XX), bp 85-100~ (30 ram). P roduc t s (XVII)-(XX) were separa ted by adsorpt ion chromatography as descr ibed above to give the i s o m e r (XVIII), a f rac t ion containing a mix ture of i s o m e r s (XVII) and (XVIII), and a f rac t ion containing a mix tu re of i s o m e r s (XIX) and (XX).

1-Methyl-3zvinY[72,8: di0xa-cisEbiq_yclo[3_3.0_]octanes (XVII) and (XVIII): Found: C 71.00; H 9,14%. CgHI~O z. Caicutated: 70.13, H 9.09%. IR s pec t rum of the mix tu re of i s o m e r s (XViI) and (XYHt) (v, em- t ) : 1650 (U=C) , 3070 (=CH).

e xocIsg_m~r iXVII). PMR spec t rum (5, ppm): 1.47 s (CHa) , 1.58-1.68 m and 1.94-2.13 m (C_H2CH20), 2.24-2.34 m (CH2CHO), 2.52-2:62 m (CH), 3.8-4.01 m (CH20), 4.18-4.27 m (CHO), 5.08 d.d (CHaHb =, J = 10 and 1.5 Hz), 5.25 d.d (CHaHb=, J = 17 and 1.5 Hz), 5.81-5.95 m (=CH, 7 lines). The PMRspec t rumof (XVII ) was s i m i t a r tc that of (II).

e n d o - I s o m e r ~_Xy_II_I)_. PMR s p e c t r u m (6, ppm): 1.50 s (CHa), 1.7-1.81 m and 2.1-2.28 m (C_HaCHaO), 1.86-1.94 m (CH2CHO), 2.52-2.62 m (CH), 3.82-4.02 m (CH20), 4.51-4.59 m (CHO), 5.06 d.d.d (CHaHb =, a = 10, 1.5, and 1 Hz), 5.20 d.d.d (CHaI-Ib~, J = 17, 1.5, and 1 HZ), 5.71-5.85 m (=CH, 7 lines). The PMR spec- t rum of (XVIII) was s i m i l a r to that of (IV). Mass spec t rum (m/z): 154 (M+).

9~* , 5S*- and 2S* , 5S* -2-VinyI-1,67dioxaspirp[4~_4]_nonanes(~X)_y(_XX__)_: Found: C 70.95; H 9.20%. CgH14(5>Calcuiated: C 70.13; H 9i09%. IR spec t rum of the mix tu re of i s o m e r s (XIX), and (XX) (v, era-l): 1650(C = C ) , 3070 (CH=). PMR s pec t rum of the mix tu re of i s o m e r s (XIX) and (XX) (5, ppm): 1.8-2.3 m (4CH2) , 5.04 d.d.d and 5.17 d.d.d (CHaH_.b =, J = 10, 1.5, 1 Hz and 17, 1.5, 1 Hz), 5.72-5.94 m (=CH, 14 lines). This spec t rum was in conformi ty with that of 2 -e thy l - l , 6 -d ioxasp i ro [4 .4 ]nonane [6]. laC NMR spec t rum (6, ppm): 24.30 and 24.42 (C_H2CH20), 30.76 and 31.44 (_CH2CHO), 34.70, 34.90 and 34.20, 35.58 (2CH 2 adjacent to the sp i ro - a tom) , 66.66 and 66.81 (CItzO), 78.62 and 80.67 (CHO), 114.69 (=CH 2 and the sp i ro -a tom) , 138.75 and 140.33 (CH =). This laC NMR spec t rum was in accordance with that of 2 - m e t h y l - i , 6-dioxaspiro[4.4]non-

ane [7].

C O N C L U S I O N S

t. Oxidative addition of acetone to bu~adiene in the p r e sence of the s y s t e m Mn(OAc)~-Cu(OAc) 2 has afforded 5 - ace toxy -5 -hep t en -2 -one , three i s o m e r i c 1 -methy l -3 , 7 -d iv iny l -2 ,8 -d io~a -c i s -b i cyc lo [3.3.0]octanes with the vinyl groups with the exo, exo, exo, endo, and endo, endo disposi t ions , and th ree d i a s t e r e o i s o m e r i c

2 ,7 -d iv iny l -1 ,6 -d ioxasp i ro[4 .4]nonanez .

2. Oxidative addition of acetopropyl alcohol and dihydrosylvart to butadiene r e su l t s in the fo rmat ion in both eases of ider~tical mix tu res of exo- and en do - l -me thy l -3 -v iny t -2 , 8 -d ioxa -c i s -b i cye Io [3 . 3 . 01oc t ane s and d i a s t e r e o i s o m e r i c 2~vinyl -1 ,6-d ioxaspi ro[4 .4]nonanes , indicating that Lhe react ion p roceeds via the same in- t e r m e d i a t e , p robab ly a complex of Mn(III) with the ketoalcohol.

1.

2. 3.

4.

5. 6.

7.

L I T E R A T U R E C I T E D

M. G. Vinogradov, M. S. Pogosyan, A. Ya. Shteinshneider , and G. I. Nikishin, [zv, Akad, 1Nauk 8SSR,

Set . Khim., 2077 (1981). M. G. Vinogradov, O. N. Pe t renko , S. P. Verenehikov, and G, 1. Nikishin, Zh. Org. Khim., 1_.55,649 (1979). V. S. Markevich , G. A. Stepanova, V. E. Nevaeva, and L. Kh. Rakhmatul ina , K h i m . - F a r m . Zh., 64

(1981). B r a u e r (editor), Manual of P r e p a r a t i v e Inorganic Chemis t ry [Russian t rans la t ion] , IL, Moscow (1966),

p. 217, (i12. W. F ranke and W. Rei th, Liebigs Ann. Chem., 1, 1 (1979). K. Mori , M. Sasaki , S. Tamada , T. Sugara, and S. Masuda, Te t rahedron , 3...55, 1601 {1979). E. Hungerbt ihler , R. Naef, D. Wasmuth, and D. Seebach, Helv. Chim. Acta, 63, 1960 (1980).

772