Synlett 2016; 27(15): 2183-2200
DOI: 10.1055/s-0035-1562360
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© Georg Thieme Verlag Stuttgart · New York

Addressing the Challenges in Suzuki–Miyaura Cross-Couplings by Ligand Design

Chengxi Li, Dongping Chen, Wenjun Tang*
  • State Key Laboratory of Bio-Organic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China   Email: tangwenjun@sioc.ac.cn
Further Information

Publication History

Received: 30 March 2016

Accepted after revision: 01 May 2016

Publication Date:
23 June 2016 (eFirst)

Abstract

Despite the increasing applicability of cross-couplings in organic synthesis, there remain many challenging issues. In the past years, we have designed and developed several classes of conformationally well-defined monophosphorus ligands: (1) bulky biaryl monophosphorus ligands such as BI-DIME and AntPhos; (2) bulky monophosphorus ligands with a second coordination site such as P,P=O ligands; (3) P-chiral monophosphorus ligands. These phosphorus ligands have enabled efficient sterically hindered aryl-aryl and aryl-alkyl cross-couplings, sterically hindered aryl-isopropyl cross-couplings, and asymmetric ary-aryl cross-couplings. The high reactivity, chemoselectivity, and enantioselectivity achieved in these reactions have allowed practical applications in total synthesis of natural products and drug molecules, leading to an efficient synthesis of a key gossypol intermediate, and, for the first time, asymmetric catalytic synthesis of korupensamine A, korupensamine B, and michellamine B.

1 Introduction

2 Sterically Hindered Aryl–Aryl Cross-Couplings

3 Sterically Hindered Aryl–Alkyl Cross-Couplings

4 Asymmetric Suzuki-Miyaura Cross-Couplings

5 Applications in the Syntheses of Natural Products and Drug Molecules

6 Conclusions