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Synlett 2011(10): 1345-1356  
DOI: 10.1055/s-0030-1260572
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Development of Bicyclo[3.3.0]octadiene- or Dicyclopentadiene-Based Chiral Diene Ligands for Transition-Metal-Catalyzed Reactions

Chen-Guo Fenga, Ming-Hua Xua,b, Guo-Qiang Lin*a
a Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China
Fax: +86(21)64166263; e-Mail: lingq@sioc.ac.cn;
b Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zuchongzhi Road, Shanghai 201203, P. R. of China
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Publication History

Received 14 February 2011
Publication Date:
23 May 2011 (online)

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Abstract

This account summarizes our efforts on the design, synthesis, and application of two classes of chiral diene ligands bearing bicyclo[3.3.0]octadiene or dicyclopentadiene skeletons. These chiral diene ligands can be readily prepared from inexpensive commercial materials with enzymatic resolution as the key synthetic step. The ligands have been successfully applied in some rhodium-catalyzed reactions, including 1,4-addition to α,β-unsaturated carbonyl compounds, arylation of imines, and conjugate addition to nitroalkenes. In addition, they have been used in the first successful palladium-diene-catalyzed asymmetric reaction.

1 Introduction

2 Preparation of Optically Active Chiral Diene Ligands

3 Preparation and X-ray Crystallography of Rhodium- and Palladium-Diene Complexes

4 Rhodium-Catalyzed Asymmetric Addition Reactions

4.1 Rhodium-Catalyzed Asymmetric Addition to α,β-Unsatu­rated Ketones and Esters

4.2 Rhodium-Catalyzed Asymmetric Addition to Imines

4.3 Rhodium-Catalyzed Asymmetric Addition to Nitroalkenes

4.4 Rhodium-Catalyzed Asymmetric Addition to α,β-Unsatu­rated γ-Lactams

5 Palladium-Catalyzed Asymmetric Suzuki-Miyaura Cross-Coupling Reactions

6 Summary and Outlook

Key words

asymmetric catalysis - diene complexes - Michael additions - cross-coupling - rhodium