Electronic control of chiral quaternary center creation in the intramolecular asymmetric Heck reaction

被引：39

作者：

Busacca, CA

Grossbach, D

Campbell, SJ

Dong, Y

Eriksson, MC

Harris, RE

Jones, PJ

Kim, JY

Lorenz, JC

McKellop, KB

O'Brien, EM

Qiu, FG

Simpson, RD

Smith, L

So, RC

Spinelli, EM

Vitous, J

Zavattaro, C

机构：

[1] Boehringer Ingelheim Pharmaceut Inc, Dept Chem Dev, Ridgefield, CT 06877 USA

[2] Boehringer Ingelheim Pharmaceut Inc, Dept Analyt Sci, Ridgefield, CT 06877 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 69卷 / 16期

关键词：

D O I：

10.1021/jo049448z

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The Boehringer-Ingelheim phosphinoimidazoline (BIPI) ligands were applied to the formation of chiral quaternary centers in the asymmetric Heck reaction. Several different substrates were examined in detail, using more than 70 members of this new ligand class. Hammett relationships were determined through systematic variation of the ligand electronics. All substrates showed essentially the same Hammett behavior, where enantioselectivity increased as the ligands were made more electron-deficient. Ligand optimization has led to catalysts which give the highest enantioselectivities reported to date for these difficult systems.

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收藏

页码：5187 / 5195

页数：9

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