Recent advances in cooperative bimetallic asymmetric catalysis: dinuclear Schiff base complexes

Shigeki Matsunaga,Masakatsu Shibasaki

doi:10.1039/c3cc47587e

Abstract

Cooperative catalysis has proven to be a powerful strategy for realizing high reactivity and selectivity in asymmetric transformations. A variety of cooperative asymmetric catalysts have been developed over the last two decades. In this feature article, recent advances from our research on cooperative asymmetric catalysis, focusing on dinuclear Schiff base catalysis, are described. Design of dinuclear Schiff base catalysts and their applications in several asymmetric C-C and C-N bond-forming reactions under simple proton transfer conditions with perfect atom-economy are discussed in detail.

Highlights

Shigeki Matsunaga is an associate professor at the University of Tokyo
When designing cooperative asymmetric catalysts, the construction of a suitable chiral environment for each targeted reaction is important for achieving efficient dual activation of nucleophiles and electrophiles through the cooperation of two metal centers
In order to broaden the scope of bimetallic cooperative asymmetric catalysis, the development of new multidentate chiral ligands is highly desirable

Summary

Introduction

Shigeki Matsunaga is an associate professor at the University of Tokyo. He was born in 1975, and received his. To induce high reactivity and stereoselectivity in the direct catalytic asymmetric C–C bond-forming reactions, the concurrent activation of pronucleophiles and electrophiles is highly desirable to control the stereochemical outcome of reactions, possibly through both Brønsted basic as well as Lewis acidic and/or Brønsted acidic sites of catalysts. One metal center together with its counter ion acts as a Brønsted base to activate pronucleophiles, while the other Lewis acidic metal center activates electrophiles Both reaction partners are simultaneously activated by fine-tuned bimetallic catalysts with an appropriate chiral environment. We highlight our own research on the development of a new family of bimetallic cooperative asymmetric catalysts, dinuclear Schiff base catalysts, and their applications in asymmetric C–C and C–N bond-forming reactions since 2007

Design of dinucleating Schiff bases

11 Isobutyl

10 Et2AlCl

Conclusions

28 Evaluation of the relative Lewis acidity of rare earth metals

31 A review on desymmetrization of meso epoxides and aziridines