Synlett 2012(4): 490-508  
DOI: 10.1055/s-0031-1290131
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Dual Activation in Organocatalysis: Design of Tunable and Bifunctional Organocatalysts and Their Applications in Enantioselective Reactions

Liang-Qiu Lu, Xiao-Lei An, Jia-Rong Chen, Wen-Jing Xiao*Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, P. R. of China
Fax: +86(27)67862041; e-Mail: wxiao@mail.ccnu.edu.cn;
Further Information

Publication History

Received 30 July 2011
Publication Date:
19 January 2012 (eFirst)

Abstract

Dual activation has been identified as an important concept in the field of asymmetric catalysis, especially asymmetric organocatalysis. A comprehensive account of the design of novel amino hydrogen-bonding organocatalysts and their successful applications in two classic carbon-carbon bond forming reactions, namely the asymmetric aldol and Michael reactions, is given. This account also covers work that uses known organocatalysts in the preparation of other important chiral molecules using the asymmetric Michael reaction as the key transformation by virtue of a dual activation strategy.

1 Introduction

2 General Concept of Dual Activation

3 Dual Activation in Asymmetric Aldol Reactions

3.1 Design and Preparation of Tunable Aminoamide Organocatalysts

3.2 Application in the Asymmetric Aldol Reaction of Cyclic Ketones with Aldehydes

3.3 Application in the Asymmetric Aldol Reaction of Acetone with Isatins

3.4 Application in the Asymmetric Aldol Reaction of Acetone with Aldehydes

4 Dual Activation in Asymmetric Michael Reactions

4.1 Design and Preparation of Tunable Aminothiourea, Aminosalicylamide, and Aminosulfamide Organocatalysts

4.2 Application in the Asymmetric Michael Reaction of Cyclic Ketones and Nitroolefins

4.3 Application in the Asymmetric Michael Reaction of Bulky Aldehydes and Nitroolefins

4.4 Other Asymmetric Michael Reactions Based on a Dual ­Activation Strategy

5 Conclusion