Toward a rational design of the assembly structure of polymetallic asymmetric catalysts: design, synthesis, and evaluation of new chiral ligands for catalytic asymmetric cyanation reactions

被引：69

作者：

Fujimori, Ikuo ^{[1
]}

Mita, Tsuyoshi ^{[1
]}

Maki, Keisuke ^{[1
]}

Shiro, Motoo ^{[2
]}

Sato, Akihiro ^{[3
]}

Furusho, Sanae ^{[3
]}

Kanai, Motomu ^{[1
]}

Shibasaki, Masakatsu ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

[2] Rigaku Corp, Tokyo 19686666, Japan

[3] JASCO Int Co Ltd, Tokyo 1920046, Japan

来源：

TETRAHEDRON | 2007年 / 63卷 / 26期

关键词：

D O I：

10.1016/j.tet.2007.02.081

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

New chiral ligands (4 and 5) for polymetallic asymmetric catalysts were designed based on the hypothesis that the assembled structure should be stable when made from a stable module 8. A metal-ligand 5:6+mu-oxo+OH complex was generated from Gd((OPr)-Pr-i)(3) and 4 or 5, and this complex was an improved asymmetric catalyst for the desymmetrization of meso-aziridines with TMSCN and conjugate addition of TMSCN to alpha,beta-unsaturated N-acylpyrroles, compared to the previously reported catalysts derived from 1-3. These two groups of catalysts produced opposing enantioselectivity even though the ligands had the same chirality. The functional difference in the asymmetric catalysts is derived from differences in the higher-order structure of the polymetallic catalysts. (C) 2007 Elsevier Ltd. All rights reserved.

引用

页码：5820 / 5831

页数：12

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