non-metathesis ruthenium-catalyzed c - c bond formation
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Non-Metathesis Ruthenium-Catalyzed C - C Bond Formation. 刘 槟 2011.5.14. 1.Reactions Involving Ruthenacycle Intermediates 2.Reactions Involving Heteroatom Additions to Alkynes 3.Reactions Involving Additions to Ruthenium Vinylidene Species 4.Diels-Alder reaction. - PowerPoint PPT PresentationTRANSCRIPT
Non-Metathesis Ruthenium-Catalyzed C-C Bond Formation
刘 槟2011.5.14
1.Reactions Involving Ruthenacycle Intermediates
2.Reactions Involving Heteroatom Additions to Alkynes
3.Reactions Involving Additions to Ruthenium Vinylidene Species
4.Diels-Alder reaction
1 Reactions Involving Ruthenacycle Intermediates
The steric interactions between the R group and the exo-methylene group of the ruthenacycle favor a conformation as depicted that forms the E isomer.
R +
OR=AcO(CH2)2
10% CpRu(COD)Cl
15% CeCl3-7H2ODMF , 60oC
81%
R
O
Ru
+ R
O
Ru
+
O
R
Ru
O
H
HR
+
Ru
O
+
HR
R
O
remove COD from rutheniumOH10%
Barry M. Trost .J. Am. Chem. Soc. 1999, 121, 4068-4069
OH
nm
+ R
O
O O
Rn m
CpRu(AN)3PF6
Ru
+
RuHNu
R
O+
m
HNu O
R
m
RuHNu
R
O+
m
Ru
R
O+
mNu
H+
H+
R
O
mNu
Barry M. Trost . J. Am. Chem. Soc. 1999, 121, 10842-10843
Alder-ene type reaction
Barry M. Trost .J. Am. Chem. Soc. 1993,115, 4361-4362
Ru
+
Ru
+
R'
RuR
+
Ru
+
RR'
RRu
+
R'R
or
RuR
+
R'
Ru
R
+
or
H
HR'
R'H
H
H
RR'
Ru
+
HR'
orR
R R'
RR'
or
R and R' =alkyl
Ru
+
Cl
-COD-Cl
H β-hydrogen elimination
Daesung Lee. J. AM. CHEM. SOC. 2005, 127, 3252-3253
OB
O+ OAc
3
RuCp(CH3CN)3PF6
acetone , 25oC70%
O
BO AcO
TrocO +
OTBS
OMe
10% CpRu(CH3CN)3PF6
acetone , rt85%
RuR'R
H3CO+
TBSO
OTrocMeO
Barry M. Trost,J. AM. CHEM. SOC. 2002, 124, 10396-10415
4
5
MeO2C
OH
CpRu(COD)Cl
MeOH , 60oC75%
RuR
+
HO
MeO2C
OO
OO
5
Barry M. Trost . J. Am. Chem. SOC. 1994,116, 4985-4986
TMS+ CO2Me
CpRu(AN)3PF6
acetone , rt88% TMS
CO2Me
only
RuTMS
R'
R
+
S RuR'
TMS
R
+
SRuTMS
R'
R
+
S
Barry M. Trost, Org. Lett., 2000 , 2 , 1761-1764
when [Ru]= CpRu(COD)Cl low yield <50%
HO
TMS
+4
HO
TMS4
TsHN
TMS
+ CO2Me7
CO2Me7
TMS
TsHN
O
TMS
+4 O
TMS4
O
DPMS
+
SMPD
O4 4
+OH [Cp'Ru(AN)3]PF6
O
CO2Et
Ru
+
OH
CO2Et
RuHO
+CO2Et
RuHO
+CO2Et
RuO
O
Takahashi, S. Chem. Lett. 1997, 1273.
[Ru]
OH
[Ru] C C CH2
C CH2
[Ru]H2O
H2O [Ru] CH
CH3
O
norborneneO
Pauson-Khand Reaction
E
E Et
[Ru] CO=15atm E
E
Et
O +E
E
E=COOMe
Take-aki Mitsudo . J. Am. Chem. Soc. 1997, 119, 6187-6188
E
E
[RuCl2(CO)3]2
toluene , CO80oC96%
E
EE=COOEt
Shinji Murai . J. Am. Chem. SOC. 1994,116, 60496050
E
E
E
EE=COOEt
[Ru] CH2Cl2
insert gas 22h rt
Ru
PCy3
PCy3
PhCl
Cl[Ru]=
insert gas = Ar yield=15 yield=99H2C CH2
Miwako Mori . J. Org. Chem. 1998, 63, 6082-6083
E
E RuE
EE
E
E
E
RuRu
Ru
RuRu
RuRu
H2C CH2
H2C CH2
Cp*Ru(COD)Cl
AcOHCOD
Ru
Cp*
OAcCl
H
RR'
O
RR'
O Ru
Cp*
Cl OAcH
RR'
O Ru
H
Cl
Cp*
OAc
O
HR R'
H
RuCp*
ClOAc
O
RR'
RR'
ORu-H
O
RR'
AcOH or EtOH
Pierre H. Dixneuf . Synlett 2000, 1, 95–97
2.Reactions Involving Heteroatom Additions to Alkynes
R + H2O +R'
O
CpRu(COD)ClNH4PF6
In(OTf)3
1:1 DMF:H2O100oC , 4h
R R'
OO
Ru
+
R
Ru
+
R
H2O
H+
Ru
+
R
OH
Ru
+
O
R
Ru
+
O
R O
R'
R'
O
Ru O
R'O
R
+
H+
R R'
OO
R= alkylR'=Me or Ph or
Barry M. Trost . J. Am. Chem. Soc. 1997, 119, 836-837
MeO2C
MeO2C
OPh
10% CpRu(AN)3PF6
CSA , H2Oacetone , rt
75%
MeO2C
MeO2C
Ph
O
O
5% CpRu(AN)3PF6
acetone , rt60%
MeO2C
MeO2CO
Ph
Barry M. Trost . J. Am. Chem. Soc. 2000, 122, 5877-5878
Ru
+
Ru
OPh
+
Ru
+
O
Ph
Ru
OPh
+HO
MeO2C
MeO2C
OPh
Ru
OPh
+H
O
MeO2C
MeO2CPh
O
O
MeO2C
MeO2CO
Ph
H2O
Ru
OPh
+
OH
MeO2C
MeO2C
MeO2CMeO2C
MeO2CMeO2C
MeO2CMeO2C
MeO2CMeO2C
Trost, B. M . Angew. Chem., Int. Ed. 2000, 39,360.
[Ru]
[Ru+]
X-R
R
[Ru+] X-
R
[Ru-X][Ru]X
R
X
R [Ru]
R'
O
R
X O
R'
R'
O
X
R O
R'
Cl- , DMFBr- , acetone
R +R'
O
CpRu(COD)Cl
15% SnCl4-H2O , R''4NClDMF , 60oC
Cl
R O
R'
major
R +R'
O
[CpRu(AN)3]PF6
15% SnBr4 , LiBracetone , 60oC
R
Br O
R'
major
Trost, B. M . J. Am. Chem. Soc. 1999, 121, 1988-1989
Pierre H. Dixneuf . Chem. Commun., 1999, 1437–1438
2 Ph + R'COOH
Cp*Ru(COD)Cl
PhPh
O2CR'
dioxane , rt
Ru
+
Ru
+
Ph Ph
Ru
2+
Ph PhH
Ru
2+
Ph PhH
H
Ru
2+
PhPh
H
H
CH3CO2
H+
CH3CO2-
PhPh
O2CCH3
3.Reactions Involving Additions to Ruthenium Vinylidene Species
NCO2t-Bu
+ OHCpRu(PPh3)2Cl
NH4PF6
100oC44%
NCO2t-Bu
O
RuPh3P Cl
Ph3P
R
PPh3
RuL
LR
RuLR
R'
OH
RuL
R'
O
R
RuL
R'
R
O
R
R
O
R' R'
OH
L
Trost, B. M . J. Am. Chem. Soc. 1990, 112, 7809-7811
bond formation occurs on the more substituted terminus of the π-allylruthenium complex
E
E
[Ru] or [Pt]
toluene , 80oC
R
E
E
R
Shinji Murai . J. Org. Chem. 2000, 65, 4913-4918
Ru
Ph
Ph
O
O
(C6F5)2P
P(C6F5)2
SbF6-
O
ROC
R
R'Z
Z
cat. 2,6-lutidine
CH2Cl2 , rtZ
Z
HCOR
R'
H
R
Ru
Ph
Ph
O
O
(C6F5)2P
P(C6F5)2
OH
E. Peter Kundig . Org. Lett.. 2010, 12, 5604-5607
4.Diels-Alder reaction
O
O
NH
OH
N N
O O NO2
O2NNO2
O2NRu
L
L
L=PPh3
1 eq tBuOOH , CH2Cl2 , 25oC , 1h O
N
OO
Ru
L
L
N
O
N
O L=OPPh3
N N
O O NO2
O2NNO2
O2NRu
L
L
L=PPh3
2 tBuOOH
-L
Ru
L
N
O
N
O
Ru
L
N
O
N
O
O
tBuOOH
tBuOH
O
O
N
O
Ru
L
N
O
N
O
O
O
NH
OH
H2O
O
N
OO
O
N
OO
Kenneth J. Shea . J. AM. CHEM. SOC. 2005, 127, 3678-3679
more Lewis acidic catalyst improved yields and ee up to 43% from 9%
the importance of intramolecularity
Incremental dilution to 7.2*10(-2) M yield up to 82% and Ee=71%
But OHN
O
OH But O N
OO
CHD
ON
O
O tBuee=9%
Ru
L
N
O
N
O Ru
L
N
O
N
ORu
L
N
O
N
O
Ru
L
N
O
N
ORu
L
N
O
N
O
R NH
OH
O
OHH
N O
OR
+R N
OO
R NO
O+
NO R
O
racemic product
racemic product
enantiomerenriched product
enantiomerenriched product