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1
Cyclopentadienyl-Ruthenium Catalysts--- One Group of Ru(II) Complexes
Huijun ZHANG
2007-07-13
2
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
3
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
4
Ruthenium Complexes
“Ruthenium complexes have a variety of useful characteristics
including high electron transfer ability, high Lewis acidity, low
redox potentials, and stabilities of reactive metallic species such
as oxometals, metallacycles, and metal carbene complexes."
Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.
Electron configuration: (Kr)4d75s1 Oxidation states: 2,3,4,6,8
5
Ruthenium Complexes
Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.
6
Cyclopentadienyl-Ruthenium Complexes
Trost, B. M.; Frederiksen, M. U.; Rudd, M. T. Angew. Chem., Int. Ed. Engl. 2005, 44, 6630
Ruthenium-Catalyzed Reactions—A Treasure Trove of Atom-Economic Transformations
7
Cyclopentadienyl-Ruthenium Complexes
Cp- and Cp*-Ru(II) Complexes:
Relationship between Structures and Reactivities:
Dérien, S.; Dixneuf, P. H. J. Organomet. Chem. 2004, 689, 1382Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006, 12, 5178
Ru
Cl
RR
R R
R
Ru
NCMeMeCNMeCN
[PF6]RR
R R
R
8
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
9
Key Features of Cp Ligands
• The M-Cp bond dissociation is large (ferrocene is
stable to 400 oC).
• The ligand blocks several coordination sites.
• The ligand tends not to get involved chemically
(although it certainly can from time to time).
• It has excellent NMR properties.
10
C5H4R
PetroleumIndustry
+rt.
~150oC
R
H
Unmethylated Cyclopentadienes
Okuda, J. Top. Curr. Chem. 1992, 160, 97.Halterman, R. L. Chem. Rev. 1992, 92, 965.
11
C5HMe4R
H
Li
2RCOOEt
R OHH+
-H2O H
R
R=Me, Et, nPr, nBu and Ph J. Organomet. Chem. 1977, 136, 1. Org. Synth. 1987, 65, 42.
R=iPr J. Organomet. Chem. 1998, 559, 181.
R=CF3 J. Am. Chem. Soc. 1992, 114, 6942.
R: containing terminal functional groups Synthesis 1993, 684.
12
C5HMe4R
R=Me J. Organomet. Chem. 1983, 243, 119. Organometallics 1988, 7, 1828. Inorg. Synth. 1992, 29, 193. .
R=CH2CH2CH=CH2 J. Organomet. Chem. 1988, 344, C1-C4.
R=tBu J. Organomet. Chem. 1996, 520, 265.
O 2 MeCHO
O
O
H+
-H2OO
1) RLi
2) H+, -H2O H
R
13
C5H2R1R2R3CO2Et
CO2Et
R1 PPh3Br
NaHCO3
CO2Et
R1 PPh3
EtO2C
R1 PPh3
R2
O
X
R3 R3
R2EtO2C
R1
Hatanaka, M; Himeda, Y.; Ueda, I. J. Chem. Soc., Chem. Commun. 1990, 526.
14
C5HR4R’
Xi, Z.; Li, P. Angew. Chem., Int. Ed. Engl. 2000, 39, 2950.
R: Me, Et, n-Pr, n-Bu, Ph···
R’CHO: aliphatic or aromatic aldehyde
Cp2ZrCl22 n-BuLi
Toluene-78oC, 1h
Cp2ZrBu22 R R
rt, 1h
ZrCp2
RR
RR
R'CHO/AlCl3
[ClAlO]
RR
RR
R'H
regioisomers about the double bonds
15
Recent Two Examples
Funami, H.; Kusama, H.; Iwasawa, N. Angew. Chem. Int. Ed. 2007, 46, 909. Lee, J. H.; Toste, F. D. Angew. Chem. Int. Ed. 2007, 46, 912.
PtCl2( 0.05 equiv)4-A M.S., ClCH2CH2Cl, rt.
R1
R4
R3
R2R2
R3
R4
R1
or Ph3PAuCl(2.0mol%), AgSbF6(2.0mol%)CH2Cl2, 0oC
16
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
17
[Ru(η5-C5R5)(MeCN)3]+ Complexes
"RuCl3 3H2O"
+ C5HMe5
[Ru(C5Me5)Cl2]2
[Ru(C5Me5)Cl]4
Ru
MeCNMeCN
NCMe
[PF6]MeOH
reflux
LiBHEt3 THF
Zn, KPF6
MeCN
KPF6MeCN
III
II
Fagan, P. J.; Ward, M. D.; Calabrese, J. C. J. Am. Chem. Soc. 1989, 111, 1698Steinmetz, B.; Schenk, W. A. Organometallics 1999, 18, 943
Mbaye, M. D.; Demerseman, B.; Renaud, J.-L.; Toupet, L.; Bruneau, C. Adv. Synth. Catal. 2004, 346 (7), 835
18
[Ru(η5-C5R5)(MeCN)3]+ Complexes
RuMeCN Ru
MeCNMeCN
NCMe
1) TlCp, rtMeCN
2) NH4PF6
Ru
[PF6]
hv.Ru
MeCNMeCN
NCMe[(C6H6)RuCl2]2[(C6H6)RuCl2]2
[PF6]
Ru
MeCNMeCN
NCMe
[PF6]COOEt
Me
R
R= Ph or Me
T. P. Gill, K. R. Mann, Organometallics 1982, 1, 485.Komatsuzaki, N.; Uno, M.; Kikuchi, H.; Takahashi, S. Chem. Lett. 1996, 677.
19
Ru(η5-C5R5)(η4-diene)Cl complexes
Ru
H
Ru
Cl
1/x [Ru(COD)Cl2]x[Ru(H2NNMe2)3(COD)(H)Cl]+
"RuCl3 3H2O"
Ru
Cl
COD = 1,5-cyclooctadiene
CpTl
CCl4
KC9H7
COD
Alvarez, P.; Gimeno, J.; Lastra, E.; Garcia-Granda, S.; Van der Maelen, J. F.; Bassetti, M. Organometallics 2001, 20, 3762
Albers, M. O.; Robinson, D. J.; Shaver, A.; Singleton, E. Organometallics 1986, 5, 2199
20
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
21
Cp-Ru Catalyzed C-C Bond Formation Reactions
• Reactions Involving Ruthenacyclopentanes,
Ruthenacyclopentenes, Ruthenacyclopentadienes
• Heteroatom Additions to Alkynes
• Reactions Involving Additions of Diazo Compounds
• Reactions Initiated by Hydrometalations
• Regioselective Allylation of Nuclephiles
• Reactions Initiated by C-H Bond Activation
22
Reactions Involving Ruthenacyclopentanes
Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 4068.
Ru
+ R'
O
RuO
R'
RuO
R'
H
R
H
+
+
RuH
O
R'
+
R
R
R
R
R'
O
R
O
R'+10% CpRuCl(cod)
15% CeCl3 7H2ODMF, 60oC
RR'
O
23
Reactions Involving Ruthenacyclopentane
+ 10% CpRu(CH3CN)3PF6
15% CeCl3 7H2ODMF, 60oC
HO
O
O
O
HO [Ru+ O
2
Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 10842.Trost, B. M.; Pinkerton, A. B.; Kremzow, D. J. Am. Chem. Soc. 2000, 122, 12007.
24
Reactions Involving Ruthenacyclopentane
Fujiwhara, M.; Nishikawa, T.; Hori, Y. Org. Lett. 1999, 1, 1635.
+ OAc
0.7% Cp*RuCl(cod)
MeOH, 100oC
OAc
[Ru+OAc
H
OAc
96
4
:
[Ru+OAc
H
H
+
+
25
Reactions Involving Ruthenacyclopentene
An Alder-Ene Type Reaction:
Trost, B. M.; Indolese, A. J. Am. Chem. Soc. 1993, 115, 4361.Trost, B. M.; Indolese, A. F.; Mu¨ ller, T. J. J.; Treptow, B. J. Am. Chem. Soc. 1995, 117, 615.
H nBu +nBu
nBunBu
nBunBu
B
L
+
B/L= 5.2/1
10% CpRu(COD)Cl
20% NH4PF6MeOH, reflux
R + R'
[Ru [Ru
[Ru+
R'
H
R
R R'R
R'
Branched Linear
[Ru+
R'
H
R
26
Reactions Involving Ruthenacyclopentene
Trost, B. M.; Müller, T. J. J. J. Am. Chem. Soc. 1994, 116, 4985.
5
MeO2C
OH10% CpRuCl(cod)
MeOH, 60oC
O
OO
O
5
[Ru+
R'
HO
MeO2C
[Ru2+
R'
HO
MeO2C-
27
Reactions Involving Ruthenacyclopentene
Trost, B. M.; Martinez, J. A.; Kulaweic, R. J.; Indolese, A. F. J. Am. Chem. Soc. 1993, 115, 10402.
4
MeO2C
10% CpRu(CH3CN)3PF6
DMF, rt
[Ru+
OH
O
CO2Me
4
O
4
CO2Me
2.3
1
:
CO2Me
H
HO
4
28
Reactions Involving Ruthenacyclopentene
De´rien, S.; Dixneuf, P. H. J. Chem. Soc. Chem. Commun. 1994, 2551.
R + OH 5% Cp*RuCl(COD)
neat, r.t., 15min
R CHO
+R
CHO
major
Ph CHO
85%(75/25)
But CHO MeOH2C CHO
60%(100/-) 70%(76/24)
29
Reactions Involving Ruthenacyclopentene
Matsushima, Y.; Kikuchi, H.; Uno, M.; Takahashi, S. Bull. Chem. Soc. Jpn. 1999, 72, 2475. Kikuchi, H.; Uno, M.; Takahashi, S. Chem. Lett. 1997, 1273.
OH
1% Cp'Ru(CH3CN)3PF6
MeOH, rtO
[Ru+HO [Ru+HO
Cp' =
CO2Et
30
Reactions Involving Ruthenacyclopentadiene
MeO2C
MeO2C 1% Cp*RuCl(cod)
O, 40oC
MeO2C
MeO2CO
Ru
+
Ru
+
R'
R
Ru
R'
R
+
Ru
+
R'
R
R'
R'
Yamamoto, Y.; Kitahara, H.; Ogawa, R.; Itoh, K J. Org. Chem. 1998, 63, 9610. Yamamato, Y.; Kitahara, H.; Ogawa, R.; Kawaguchi, H.; Tatsumi, K.; Itoh, K.
J. Am. Chem. Soc. 2000, 122, 4310.
31
Heteroatom Additions to Alkynes
5% CpRuCl(cod)
NH4PF6, In(OTf)3
DMF/H2O 1/1, 100oC
NC(H2C)3
O
+NC(H2C)3
O O
Additions of Water
Trost, B. M.; Krause, L.; Portnoy, M. J. Am. Chem. Soc. 1997, 119, 11319.
Ru
+
Ru
Ru
+
+
Ru O
R'
+
R
O
R' R
R
H2O
H+
Ru
+
OH
R
R
OR'
O
Ru
+
R
O R'
O
O
H+
R
O
32
Heteroatom Additions to Alkynes
Ru
+
OR'
R
Ru
R
R'O H2O
Ru
R
R'O
HO
Ru
R
R'O
O
H
+ +
+
R'
RO
O
ORu
R'
R+
O
R'
R
Intramollecular Version
O
Ph
H3CO2C
H3CO2C
10% CpRu(CH3CN)3PF6
CSA, H2Oacetone, rt
5% CpRu(CH3CN)3PF6
acetone, rtO
Ph
O
O
Ph
H3CO2CH3CO2C
H3CO2CH3CO2C
Trost, B. M.; Brown, R. E.; Toste, F. D. J. Am. Chem. Soc. 2000,122, 5877.
33
Heteroatom Additions to Alkynes
Additions of Halides
Ru+ + X- R+
R
Ru+X-
R
RuXX Ru
R
O
R
X
O
Z
R Ru
X
O
X
R
O
E
Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 1988.
CN
O
10% CpRuCl(cod)
SnCl4,5H2O, N(CH3)4ClDMF, 60oC8.2:1, E:Z
+
CN
Cl
O
34
Heteroatom Additions to Alkynes
Additions of Carboxylic Acids
Cp*RuCl(cod)
dioxane, rt+
H3CO
CH3COOH O2CCH3
H3CO
OCH3
Le Paih, J.; Monnier, F.; Dérien, S. J. Am. Chem. Soc., 2003, 125, 11964.
Ru
+
R
CH3CO2H
Ru
R
R
-O2CCH3
Ru
+
R RRu
+
R
H
H3CCO2
RR
H
2+
R
O2CCH3
35
Reactions Involving Additions of Diazo Compounds
Me3Si
SiMe3
OH
N2
SiMe3 5% Cp*RuCl(cod)
dioxane, 60oC+2
OH
Le Paih, J.; Dérien, S.; Özdemir, I.; Dixneuf, P. H. J. Am. Chem.Soc. 2000, 122, 7400.
Ru
Cl
RuClSiMe3
RuClSiMe3
R R'
RuClSiMe3
R R'
RuCl
RSiMe3
R'
SiMe3
N2
SiMe3
Me3Si
SiMe3
R'
R
R R'
R R'
N2SiMe3
36
Reactions Initiated by Hydrometalations
Le Paih, J.; Rodrı´guez, D. C.; De´rien, S.; Dixneuf, P. H. Synlett 2000, 95.
OPh
5% Cp*RuCl(cod)
EtOD, rtO
Ph
Ru D
O
DPh
Ru O
Ph
Ru
H
D
D
O
RuPh
D
37
Regioselective Allylation of Nuclephiles
OCO2Me + HNCp*RuCl(COD)
0oC, THF
N
Ph
Ph N+
84 16
(overall yield 99%)
B L
:
Ph OCO2tBu
+
NaCH(CO2Me)2
1% catalyst
DMF, rt.Ph
MeO2C CO2Me
PhCO2Me
CO2Me
+
B L
[Cp*Ru(NCCH3)3]PF6
[CpRu(NCCH3)3]PF6 1 2
9 1
Trost, B. M.; Fraisse, P. L.; Ball, Z. T.; Angew. Chem. Int. Ed. 2002, 41, 1059.
Kondo, T.; Ono, H.; Satake, N.; Mitsudo, T.; Watanabe, Y. Organometallics 1995, 14, 1945.
38
Oxidative Addition of Allylic Substrate
Key Step in Ruthenium-Catalysed Allylic Substitution Reactions
Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006, 12, 5178
RuX
XPh
Ru
X LL
2 L
Ph XNu-
Ph
Nuand
Ph Nu
2 L
X-
39
Planar Chiral Ruthenium Catalysts
Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S.J. Am. Chem. Soc. 2001, 123, 10405.
Ph Ph
OCO2Et
NuNaPh Ph
Nu
63% ee 97%
RO
O
PRu
Ar Ar
MeCNMeCN
[PF6]
(5 mol%)
THF, 20oC, 6h
>
+
>
NuNa= NaCH(CO2Me)2, NaCH(CO2Et)2, NaCMe(CO2Me)2R= Me, Ph, tBu; Ar= Ph, o-MeC6H4, 3,5-Me2C6H3
40
Reactions Initiated by C-H Bond Activation
TBDMSOCOOEt 10% CpRu(CH3CN)3PF6
DMF, rt
COOEtTBDMSO
Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 9728.
Ru
+
Ru
+
+
COOEt
COOEt
Ru
+
COOEt
H
EtOOC
RuH
EtOOCTBDMSO
TBDMSO
TBDMSO
TBDMSO
TBDMSO
Ru
TBDMSOCOOEt
+
41
Content
Introduction
Cyclopentadienes
Cyclopentadienyl-Ruthenium
Their Applications
Outlook
42
Outlook
• New sterically demanding catalysts with bulky, electron
rich C5R5 ligands
• New optically active catalysts with chiral C5R4R* ligands
• Polymerizable catalysts for the recovery and recycling of
catalysts.
R
R
R
R
R[Ru
[Ru: RuCl(COD), Ru(NCMe)3+, RuHL2
R
R
R
R[Ru
R3
R1
R2*
[Ru
R
RR
R
n
etc.
“Teaching An Old Dog New Tricks”
43
Acknowledgement
Laboratoire de Catalyse et Organométalliques
Prof. Zhenfeng Xi, Prof. Zhiping LiProf. Pierre Dixneuf, Dr. Christian Bruneau,
Dr. Bernard Demerseman
All Professors in the Institute of Organic Chemistry
All my lab mates
Peking U. Team: Rennes U. Team:
44
Thank you for your attention!
45
Proposed Mechanism
ZrCp2
R
HO L.A.
path a
path b
Cp2ZrCl2
L.A.
R
H
O
ZrCp2
R
O
ZrCp2
O
RL.A.
Cp2Zr=O
L.A.
R
H
OL.A.
R[ClAl=O]n
R
H
46
Ruthenium Hydride
RuIIClLn
¦Â-H elimination
-CH3CHO-H+
- ClRuIILn
+ CH3CH2OH H3CHC OH
H RuIILn
+
H
RuIILn
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