Organocatalytic Asymmetric Hydrophosphonylation/Mannich Reactions Using Thiourea, Cinchona and Brønsted Acid Catalysts

Dedicated to Anupa Bhadury on the occasion of her 45th birthday.

Abstract

This account summarizes the results of recent studies conducted in our group on the development of chiral thiourea/cinchona and Brønsted acid derived bifunctional organocatalysts. Selected asymmetric organocatalytic transformations were targeted to obtain enantioenriched bioactive products. Special emphasis was placed on the preparation of environmentally friendly anti-plant viral agents such as enantiomerically enriched α-aminophosphonates and methods to assess the enantiomeric purity of these products on selected chiral stationary phases. The review also tries to delineate the underlying mechanism of various asymmetric transformations by BINOL-phosphoric acid-induced activation of imines and to make unambiguous assignments of the absolute configuration of α-aminophosphonates obtained from organocatalytic hydrophosphonylation of pregenerated and in situ generated imines.

1 Introduction

2 BINOL-Derived Brønsted Acid Organocatalysts and Their Applications

2.1 Two-Component Reaction

2.2 Three-Component Reaction

2.3 Analytical Aspects

2.4 Absolute Configuration and Proposed Mechanism

3 Chiral Thiourea/Cinchona Derived Bifunctional Organocatalysts and Their Applications

4 Ongoing Activities

5 Concluding Remarks

Key words

chirality - enantioselectivity - diastereoselectivity - organocatalysts - Brønsted acids - absolute configuration

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