Synthesis of Bulky and Electron-Rich MOP-type Ligands and Their Applications in Palladium-Catalyzed C−N Bond Formation

Xiaomin Xie,† Tony Y. Zhang,†§ and Zhaoguo Zhang*†‡
School of Chemistry and Chemical Engineering, Shanghai Jiaotong University, 800 Dongchuan Road, Shanghai 200240, China, State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 354 Fenglin Road, Shanghai 200032, China, and Chemical Product R&D, Eli Lilly and Company, Indianapolis, Indiana 46285-4813
J. Org. Chem., 2006, 71 (17), pp 6522–6529
DOI: 10.1021/jo060945k
Publication Date (Web): July 12, 2006
Copyright © 2006 American Chemical Society
†

 Shanghai Jiaotong University.

,
§

 Eli Lilly and Company.

,
*

 To whom correspondence should be addressed. Phone:  +86-21-5474-8925. Fax:  +86-21-5474-1297.

,
‡

 Shanghai Institute of Organic Chemistry.

, zhaoguo@sjtu.edu.cn

Abstract

Abstract Image

A series of 2-dialkylphosphino-2‘-alkoxy-1,1‘-binaphthyl ligands (6a−c and 8a−c) have been prepared conveniently by a lithium-initiated ring-opening reaction of dinaphthofuran, followed by selective phosphorylation. These compounds displayed a remarkable air and moisture stability, both in solid form and in solution. Application of these phosphine ligands in palladium-catalyzed C−N bond forming reactions revealed the crucial roles of the steric bulk of the substituents on the phosphorus atom governing the catalytic activity. Specifically, 2-di-tert-butylphosphino-2‘-isopropoxy-1,1‘-binaphthyl (8b) proved to be the most effective for the aminations of aryl halides with primary amines, while the less bulky 2-dicyclohexyl-2‘-methoxy-1,1‘-binaphthyl (6a) was more effective for the aminations with secondary amines. The steric and electronic effects of the ligands were analyzed to account for these observations.

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History

  • Published In Issue August 18, 2006
  • Received May 7, 2006

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