STUDIES OF ALLYLIC SUBSTITUTION CATALYZED BY A PALLADIUM COMPLEX OF A C-2-SYMMETRICAL BIS(AZIRIDINE) - PREPARATION AND NMR SPECTROSCOPIC INVESTIGATION OF A CHIRAL PI-ALLYL SPECIES

被引：103

作者：

ANDERSSON, PG ^{[1
]}

HARDEN, A ^{[1
]}

TANNER, D ^{[1
]}

NORRBY, PO ^{[1
]}

机构：

[1] ROYAL DANISH SCH PHARM,DEPT MED CHEM,DK-2100 COPENHAGEN,DENMARK

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 1995年 / 1卷 / 01期

关键词：

ASYMMETRIC CATALYSIS; AZIRIDINES; CHIRAL LIGANDS; PALLADIUM COMPOUNDS;

D O I：

10.1002/chem.19950010106

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The chiral palladium pi-allyl intermediate for the catalytic asymmetric synthesis shown in Scheme 1 has been isolated as the PF6- salt. MM2 calculations have been performed and the structure of the palladium complex in solution has also been investigated by means of NMR spectroscopy. Both the computational and spectroscopic results suggest that in the complex the bidentate bis(aziridine) ligand adopts a conformation that forces the pi-allyl moiety out of the normally preferred square-planar geometry. This nicely explains the very high enantioselectivity observed in the title reaction.

引用

页码：12 / 16

页数：5

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