• Masakatsu Shibasaki was born in 1947 in Japan. In 1974 he received his Ph. D. Degree from the University of Tokyo. After then he did postdoctoral studies with professor E. J. Corey at Harvard University. In 1977, he returned to Japan and joined Teikyo University as an associate professor. In 1983 he moved to Sagami Chemical Research Center as a group leader and in 1986 took up a professorship at Hokkaido University, before returning to the University of Tokyo as a professor in 1991.His research interests include asymmetric catalysis and medicinal chemistry of biologically significant compounds.

• He has received Fluka Prize( 1996), the Elsevier Award for Inventiveness in Organic Chemisty(1998), the Pharmaceutical Society of Japan Award(1999), ACS Award (2002), the National prize of Purple Ribbon(2003), Japan Academy Prize(2005), t he Rare Earth Society of Japan Award(2006), ACS Award for Creative Work in Synthetic Organic Chemisty(2008), Centenary medal and lectureship (2008), Prelog Award Medal(2008), and many others.

Bifunctional catalysts

Advantage：Mild Reaction Condition Enhanced Catalytic Activity

Higer Levels of Stereodifferentiation

Shibasaki, M. J. Am. Chem. Soc.1993, 115, 10372

N

O

O

N

O

O

*

M1

M2

NOBoc

R

NHBoc

H NOBoc

NO2

R

Hor

M1=M2=Ni

N

NO2Ph

Me

O

Boc

M1=M2=Mn

up to 96% ee

1,4-addition

N

OR1

Bn

NR2R3

OH

addition

up to 98% ee

M1=Ga M2=Yb

aza-henry Reaction

PhMe

NH

NHAc

Boc

up to 97% ee

M1=Cu M2=Sm

O

H3C

O

ROOC

1,4-addition

up to 99% ee

M1=M2=Co

O

P(OEt)2Ph

NHBoc

O

up to 99% ee

M1=M2=Ni

Mannich-Type

Nitroaldol

ROCH3

OCH3

NO2

OH

NHBoc

dr 10:1:traceM1=PdM2=La

NO

NX NH

Boc Boc

BocUp to 99% ee

M1=M2=Ni up to 99% ee

Bimetallic Schiff Base catalysts

Bimetallic Schiff Base catalysts M1=Cu M2=Sm

Shibasaki, M. J. Am. Chem. Soc. 2010, 132, 4925.

Shibasaki, M. J. Am. Chem. Soc. 2007, 16, 4900.

M1=Pd M2=La

Shibasaki, M. etal. Ang. Chem. Ind. Ed. 2008, 47, 3230.Shibasaki, M. etal. Org. Lett. 2008, 10, 2231.

M1=M2=Ni

Shibasaki, M. J. Am. Chem. Soc. 2008, 130,2171.

Shibasaki, M. J. Am. Chem. Soc. 2009, 131,9169.

M1=M2=Mn

Disadvantage:1, 10 mol % catalyst was required. 2, only 3-benzyl type substituted oxindoles

afforded than 90% ee. 3, the key N-N cleavage of amination adduts

was not reported.

Chen, Y.-J. Org. Lett. 2009,11, 3874.

first organacatalytic enantioseletive amination of oxindoles

Shibasaki, M. J. Am. Chem. Soc. 2010, 132, 1255.

Shibasaki, M. J. Am. Chem. Soc. 2010, 132, 3666..

dr >30:1up to 99% ee

dr>30:1up to 99% ee

Direct catalytic asymmetric vinylogous reactions of an α,β-unsaturated γ-butyrolactam as a donor are described. A homodinuclear Ni2-Schiff base complex promoted a vinylogous Mannich-type reaction of N-Boc imines as well as a vinylogous Michael reaction to nitroalkenes selectively at the γ-position under simple proton-transfer conditions. Vinylogous Mannich adducts were obtained in 5:1→30:1 dr and 99% ee, and vinylogous Michael adducts were obtained in 16:1→30:1 dr and 93−99% ee.

M1=Ga,M2=Yb

Zhu, J., Org. Lett. 2007, 9, 3615.

ee 50%-80％

Shibasaki, M. J. Am. Chem. S. 2009, 131, 8384.

Possible Reaction Mechanisum

M1=M2=Co

Jфrgensen, K. A. J. Am. Chem. Soc. 2004, 26, 5672.

Maruoka, K., J. Am. Chem. Soc. 2007, 129, 1038.

First Enantioseletive Conjugate to Alkyones

Shibasaki, M. Ang. Chem. Int. Ed. 2009, 48, 2218.

Postulated catalytic cycle of the Reaction Shibasaki, M. Molecules, 2010, 15, 532.