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Hydrogenationheterogeneous
(catalytic)hydrogenation
g
homogeneous
oxidation state: Rh(I)valence electrons: 16e
Wilkinson’s catalyst catalyst for y yhydrogenation (1966)
Heterogeneous Pd Catalysts for Hydrogenation
大野桂二、佐治木弘尚, Organic Square (Wako) 2008, 22, 2.
Wilkinson’s catalyst RhCl(PPh3)3
R R R R R R
R R
RhCl(PPh3)3(cat )(cat.)
H2
CO2Me CO2Me CO2Me96% 4%
PtO2 or Pd/BaSO4(cat )
>49% 26%
(cat.)H2
Birch, A. J.; Williamson, D. H. Org. React. 1976, 24, 1.
Catalytic Cycle ◆dihydride◆hydrogen-first mechanism
RhL L
Cl LCl
H oxidativeRh
L S
Cl L
H2
H
R
H oxidative addition
reductive
L HH
LH
H
reductive elimination
RhL H
Cl LS
RhL
Cl LS
H
R
RhL H
H
i ti RCl L
R
insertionturnover-limiting step
Crabtree’s catalyst
TOF (h–1) of hydrogenationTOF (h ) of hydrogenation
Crabtree, R. Acc. Chem. Res. 1979, 12, 331.
mechanism: Ir(III) and Ir(V) rather than Ir(I) and Ir(III) ?Hall, M. B.; Burgess, K. Chem. Eur. J. 2005, 11, 6859.
TON = turnover number = moles of product / moles of catalystTOF = turnover frequency = TON / time
Directing EffectsOH, CO2Me, C=O, or OMe
Stork, G.; Kahne, D. E. J. Am. Chem. Soc. 1983, 105, 1072., ; , , ,
Crabtree, R. H.; Davis, M. W. J. Am. Chem. Soc. 1986, 51, 2655.
Catalytic Asymmetric HydrogenationH
Cy
PhCO2H
NHAc
H2RhBF4[((R)-camp)2(cod)] (cat.)
PhCO2H
NHAc (R)-CAMP
PMe
OM88% ee OMe
H2 O PPhPh
CO2H
NHAc
2RhCl[(R,R)-diop] (cat.)
PhCO2H
NHAc85% ee
(R,R)-DIOP
O
O PPh2
PPh2
85% ee
H2
PhCO2H
NHBz
[Rh((R)-binap)(MeOH)2]+ClO4– (cat.)
PhCO2H
NHBz100% ee
PPh2
PPh2
100% ee(R)-BINAP
「演習で学ぶ有機反応機構」化学同人 A019
CyNMe2
Akabori, S. et al. Nature 1956, 178, 323.
CAMP
PMe
OMePh
PMe
Bu
Horner et al (1968)
O
O PPh2
PPh2
DIOP
FePPh2
PPh2
BPPFACAMPKnowles, et al. (1972)
Horner, et al. (1968)Knowles, et al. (1968)
DIOPKagan, et al. (1971)
BPPFAHayashi, Kumada, et al. (1974)
Ph PC6H4-2-OMe
PPh2
PPh2
N
Ph2P
PPh
PPh2
PPh
P
PC6H4-2-OMe
Ph
BINAPNoyori, et al. (1980)
Boc PPh2
BPPMAchiwa (1976)
PPh2
chiraphosBosnich, et al. (1977)
Ph
DIPAMPKnowles, et al. (1975)
Catalytic Cycle◆dihydride P
Rh
Ph B'y
◆olefin-first mechanism RhPO
NRO2C
H
PhCO2R
NHAc PPhA
BP
RhP
SS
NHAc PRh
P ON
CO2R
HH
H2
PhCO2R
NHAc
turnover-limiting step
2
PPhH
P
Ph
CO RH C
D
RhP
O NCO2R
H
HP
RhP O N
CO2RH
S
Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley & Sons: New York, 1994.Cf.) For hydrogen-first mechanism in cationic Rh catalysis: Gridnev, I. D.; Imamoto, T. Acc. Chem. Res. 2004, 37, 633.
Curtin–Hammett Principle
Seeman, J. I. et al. J. Am. Chem. Soc. 1980, 102, 7741.
Enantioselective Isomerization
NEt27 tons
P
R RP
RR
Rh ClO4
P
R RP
RR
4
R = Me
NEt2
99% i ld
6.7 kg
99% yield98.5% eeTON = 8000
OH (–)-menthol
Tani, K.; Yamagata, S.; Akutagawa, S.; Kumobayashi, S.; Takemoto, T.; Takaya, H.; Miyashita, A.; Noyori, R.; Otsuka, S. J. Am. Chem. Soc. 1984, 106, 5208. 芥川進 有合化 1986, 44, 513.
Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley & Sons: New York, 1994.
◆monohydrideCatalytic Cycle
Morris, R. H. In Handbook of Homogeneous Hydrogenation; de Vries, J. G.; Elsevier, C. J., Eds.; Wiley-VCH: Weinheim, 2007.
Hydrogenation of Ketones
Enantioselective Hydrogenation
Kinetic Resolution
Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley & Sons: New York, 1994.
Dynamic Kinetic Resolution (DKR)
100% conversion, dr = 99:1, 92% ee
OMe
OO
OMe
OHO
OMe
OHO
+
major minor
OO OHO OHO
OMe OMe OMe+
Noyori, R. et al. J. Am. Chem. Soc. 1989, 111, 9134.
Route to a Key Intermediate of Carbapenem
O
OMe
O H2Ru(II)-cat.
OH
OMe
O 1) HCl2) NaOH
OH
OH
O
NHBz NHBz NH2
PPh
DKR
PPh3
OTBSTBSClimi.
RuCl3·nH2OAcO2HAcONa
OTBSOAc
NO H
NO H
Shimizu, H. et al. Acc. Chem. Res. 2007, 40, 1385.
BINAP/1,2-Diamine–Ru(II) Complex
OH2 (8 atm)
catalyst (0.2 mol%)
OH catalyst =
R2P Cl H2
N Ph
100% yield
PR2
Ru
Cl NH2
N
Ph
+ KOH
96% eeR = 4-tolyl
OO
H H
P
PRu
H
X N
H2N
P
PRu
X N
HN
X H2H2
X NH2
For mechanistic studies, see: Noyori, R. et al. J. Am. Chem. Soc. 2003, 125, 13490.Bergens, S. H. et al. J. Am. Chem. Soc. 2008, 130, 11979.
Asymmetric Transfer Hydrogenation
T
NPh
Ts
RuO OHN
H2Ph Cl
(0.5 mol %)KOH (0.6 mol%)
O OH
>99% yield97% ee
Noyori, R. et al. J. Am. Chem. Soc. 1997, 119, 8738.
97% ee2-propanol
28 °C
NPh
Ts
R
NH2
Ph
Ru
Cl
(0.1 mol %)HCO H / Et N
O OHHCO2H / Et3N
100% yielddl : meso = 98 6 : 1 4
DMF40 °CO OH
dl : meso = 98.6 : 1.4>99% ee
Ikariya, T. et al. Org. Lett. 1999, 1, 1119.
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