1-phosphino-2-sulfenylferrocenes as planar chiral ligands in enantioselective palladium-catalyzed allylic substitutions

被引：120

作者：

Mancheño, OG ^{[1
]}

Priego, J ^{[1
]}

Cabrera, S ^{[1
]}

Arrayás, RG ^{[1
]}

Llamas, T ^{[1
]}

Carretero, JC ^{[1
]}

机构：

[1] Univ Autonoma Madrid, Fac Ciencias, Dept Quim Organ, E-28049 Madrid, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 09期

关键词：

D O I：

10.1021/jo0340657

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis of a wide structural variety of enantiopure 1-phosphino-2-sulfenylferrocene ligands 1 possessing exclusively planar chirality is described. In the case of the readily available tert-butylsulfenyl derivatives very high enantioselectivities were obtained in the palladium-catalyzed allylic substitution of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate (ee's up to 97%) and nitrogen nucleophiles (ee's up to 99.5%). Palladium complexes of these ferrocenes were characterized by NMR and X-ray diffraction, revealing the P,S-bidentate character of the ligands 1 and the formation: of a single epimer on the stereogenic sulfur atom resulting from the complexation with palladium. A model justifying the observed asymmetric induction exerted by this novel family of chiral ferrocenes, supported by solution NMR studies on a palladium allylic complex, is discussed.

引用

页码：3679 / 3686

页数：8

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