TRANSITION METAL -CATALYZED HOMOGENEOUS ASYMMETRIC HYDROGENATION - Catalytic Asymmetric Synthesis - page 375

Chiral Rh catalyst

∗

COOR

COOR

ROOC ROOC

% ee
(Confi g.) Ligand R S / C Reaction Condition a Reference

( R ) - BICHEP H 1,000 EtOH, 25 ° C, 1 atm H 2 96 ( R ) 77c

( R,R ) - Et - DuPhos Me 10,000 MeOH, 25 ° C, 5 atm H 2 98 ( R ) 28g

( S,S ) - Et - BPE Me 5,000 MeOH, 28 ° C, 10 atm, 30 min 95 ( R ) 3 2

( R,R ) - Ph - BPE Me 100,000 MeOH, 25 ° C, 10 bar H 2 99 ( S ) 3 2

( R,R ) - UlluPhos Me 1,000 MeOH, 27 ° C, 2 atm, 2.8 h > 99.5 ( S ) 181

112 Me 1,000 CH 2 Cl 2 , rt, 1 atm > 99.9 ( S ) 182

( S,S,S,S ) - 26 H 100 MeOH, rt, 1 atm, 24 min,

50%

98.0 ( R ) 78a

Me 100 MeOH, rt, 1 atm, 9 min, 50% 98.9 ( R ) 78a

( R,R ) - Cat AS ium M H 10,000 CH 2 Cl 2 , 25 ° C, 8 atm, 3 h 99 ( S ) 29b

Me 500 MeOH, 25 ° C, 4 atm, 3 h,

1.0 eqiuv i Pr 2 NEt

98 ( S ) 29b

Et - 35 H 100 MeOH/H 2 O(3:97), rt, 10 atm

H 2

> 99 ( R ) 68b

27 Me 100 MeOH, rt, 1 atm H 2 99.1 ( R ) 78a

( R,R ) - 30 H 100 MeOH, 25 ° C, 1 atm, 96.9 ( R ) 78b

Me 100 MeOH, rt, 1 atm H 2 97.9 ( R ) 4 7

( R,R ) - ( S,S ) - Et -
TRAP

Me 200 CH 2 Cl 2 , refl ux, 1 atm H 2 96 ( S ) 54c

92 Me 100 MeOH, rt, 1 atm H 2 98 ( S ) 82a

93 Me 100 MeOH, rt, 1 atm H 2 98 ( R ) 168

( S,S ) - Et -
FerroTANE

Me 200 MeOH, rt, 5.5 atm H 2 98 ( R ) 183

( S,S,S,S ) - f -
KetalPhos

H 100 MeOH, rt, 80 psi H 2 99.5 ( R ) 5 5

102 Me 100 MeOH, rt, 1 atm H 2 95 ( R ) 184

( S,S ) - Ad - BisP * Me 500 MeOH, rt, 1.6 atm H 2 99.6 35b

( S,S,R,R ) - TangPhos Me 5,000 THF, rt, 20 psi H 2 99 ( S ) 36c

( R,R,S,S ) -
DuanPhos

Me 100 THF, rt, 20 psi H 2 > 99 ( S ) 3 7

( R,R ) - 105 Me 5,380 CH 2 Cl 2 , rt, 1.3 bar H 2 > 99.5 ( R ) 6 2

120 Me 1,000 CH 2 Cl 2 , − 10 ° C, 0.3 bar H 2 98.7 ( R ) 185

98 H 100 MeOH, rt, 300 psi H 2 97.4 ( R ) 9 2

Me 10,000 CH 2 Cl 2 , rt, 10 bar H 2 93a

( S C , R P , S a ) - 103 99.1 ( S )

H 20 CH 2 Cl 2 , 25 ° C, 1 atm H 2 149

( S ) - MonoPhos 96.6 ( S )

Me 5,000 CH 2 Cl 2 , 20 ° C, 1.3 atm H 2 186a

( S ) - ( R ) - 59 97.4 ( S )

Me 40,000 CH 2 Cl 2 , 23 ° C, 20 bar H 2 187

( S ) - 62 96.9 ( S )

63 Me 100 CH 2 Cl 2 , rt, 10 atm H 2 99.4 ( R ) 188

i PrOH, 20 ° C, 1.1 atm H 2 ( R,R ) - 64 H 100 96.0 ( S ) 4 8

( S,S ) - Quinox Me 1,000 MeOH, 25 ° C, 10 bar 99.8 ( S ) 5 3

a Complete conversion unless otherwise noted.

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