CATALYTIC ASYMMETRIC-SYNTHESIS OF OPTICALLY-ACTIVE ALCOHOLS VIA HYDROSILYLATION OF OLEFINS WITH A CHIRAL MONOPHOSPHINE-PALLADIUM CATALYST

被引：51

作者：

HAYASHI, T ^{[1
]}

UOZUMI, Y ^{[1
]}

机构：

[1] HOKKAIDO UNIV,GRAD SCH PHARMACEUT SCI,SAPPORO,HOKKAIDO 060,JAPAN

来源：

PURE AND APPLIED CHEMISTRY | 1992年 / 64卷 / 12期

关键词：

D O I：

10.1351/pac199264121911

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Axially chiral monophosphines 1, (S)-2-(diphenylphosphino)-2'-methoxy-1,1'-binaphthyl (MOP, 1a) and its analogs substituted with isopropoxy (1b), benzyloxy (1c), and ethyl (1d) at 2' position, were prepared. Reaction of simple terminal alkenes 5 (RCH=CH2: R = n-C4H9, n-C6H13, n-C10H21, PhCH2CH2, cyclo-C6H11) with trichlorosilane at 40-degrees-C in the presence of 0.1 or 0.01 mol % of palladium catalyst prepared in situ from [PdCl(pi-C3H5)]2 and (S)-1a proceeded with unusual regioselectivity (up to 94%) and with high enantioselectivity to give high yields of 2-(trichlorosilyl)alkanes 6 together with a minor amount of 1-(trichlorosilyl)alkanes 6'. Oxidation of the carbon-silicon bond gave optically active alcohols 8 (RCH(OH)CH3), enantiomeric purity ranging between 94% and 97% ee. The high enantioselectivity was also observed in the enantioposition-selective hydrosilylation of norbornene (9) and related meso bicyclic olefins catalyzed by the MOP/palladium, which gave exo-2-norbornanol (11) and related alcohols with up to 96% ee.

引用

页码：1911 / 1916

页数：6

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