Regio- and Enantioselective Catalytic Monoepoxidation of Conjugated Dienes: Synthesis of Chiral Allylic cis-Epoxides

被引：19

作者：

Jat, Jawahar L. ^{[1
]}

De, Saroj Ranjan ^{[1
]}

Kumar, Ganesh ^{[1
]}

Adebesin, Adeniyi Michael ^{[1
]}

Gandham, Shyam K. ^{[1
]}

Falck, John R. ^{[1
]}

机构：

[1] Univ Texas SW Med Ctr Dallas, Div Chem, Dept Biochem, Dallas, TX 75390 USA

来源：

ORGANIC LETTERS | 2015年 / 17卷 / 04期

关键词：

AQUEOUS HYDROGEN-PEROXIDE; ASYMMETRIC EPOXIDATION; SHARPLESS EPOXIDATION; ARACHIDONIC-ACID; EPOXY ALCOHOLS; FATTY-ACIDS; OLEFINS; HYDROPEROXIDE; COMPLEXES; DIHYDROXYLATION;

D O I：

10.1021/acs.orglett.5b00281

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Ti(IV)-salan 4 catalyzes the diastereo- and enantioselective monoepoxidation of conjugated dienes using 30% H2O2 at rt or below even in the presence of other olefins and adjacent stereocenters. Its enantiomer, ent-4, provides access to the opposite diastereomer or enantiomer. The resultant chiral allylic epoxides, and the triols derived from them, are versatile synthetic intermediates as well as substructures present in many bioactive natural products. The epoxidation is highly specific for Z-olefins. For 1-acyl(silyl)oxypenta-2,4-dienes, epoxidation of the distal olefin is generally favored in contrast to the adjacent regioselectivity characteristic of Sharpless, peracid, and other directed epoxidations of hydroxylated dienes.

引用

页码：1058 / 1061

页数：4

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