Design of Highly Functional Small-Molecule Catalysts and Related Reactions Based on Acid-Base Combination Chemistry

Abstract

The design of small but highly functional artificial catalysts is very important for practical organic synthesis. We have ­succeeded in the rational design of small and simple catalysts and related reactions based on acid-base combination chemistry. Acid-base combined catalysts can be classified into three types: (i) acid-base combined salt catalysts, (ii) conjugate acid-base catalysts, and (iii) nonconjugate acid-base catalysts. We have systematically developed acid-base combined salt catalysts such as ammonium salts, ate complexes, ion pairs and cation-π complexes, acid-base conjugate catalysts such as metal oxides (monoconjugation) and zinc(II)-3,3′-diphosphinol-BINOLates (triconjugation), and acid-base nonconjugate catalysts like l-histidine-derived sulfonamides.

• 1 Introduction

• 2 General Concept for the Design of Catalysts Based on Acid-Base Combination Chemistry

• 3 Catalytic Dehydrative Monoesterification of Phosphoric Acid with Alcohols Based on Acid-Base Combination Chemistry

• 4 Acid-Base Combined Salt Catalysts (Type A)

• 4.1 Brønsted Acid-Brønsted Base Combined Salt Catalysts (Type A-1)

• 4.2 Lewis Acid-Lewis Base Combined Salt Catalysts and Reagents (Type A-2)

• 4.3 Cation-Anion-Pair Catalysts (Type A-3)

• 4.4 Cation-π Complex Catalysts (Type A-4)

• 5 Lewis Acid-Lewis Base Conjugate Catalysts (Type B)

• 5.1 Molybdenum Oxides as Highly Effective Dehydrative ­Cyclization Catalysts Directed toward the Synthesis of ­Oxazolines and Thiazolines (Type B-1)

• 5.2 Zinc(II)-3,3"-Diphosphinoyl-BINOLates in the ­Asymmetric Addition of Organozinc Reagents to ­Aldehydes (Type B-2)

• 6 Brønsted Acid-Lewis Base Nonconjugate Asymmetric Catalysts (Separated Type) (Type C)

• 6.1 l-Histidine-derived Sulfonamide as a Minimal Artificial Acylase for the Kinetic Resolution of Racemic Alcohols

• 7 Conclusions

catalysis - salt - conjugate - acid-base combination chemistry - asymmetric synthesis

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