Regio- and Stereoselective Monoepoxidation of Dienes using Methyltrioxorhenium: Synthesis of Allylic Epoxides

被引：11

作者：

De, Saroj Ranjan ^{[1
]}

Kumar, Ganesh ^{[1
]}

Jat, Jawahar L. ^{[1
]}

Birudaraju, Saritha ^{[1
]}

Lu, Biao ^{[1
]}

Manne, Rajkumar ^{[1
]}

Puli, Narender ^{[1
]}

Adebesin, Adeniyi Michael ^{[1
]}

Falck, John R. ^{[1
]}

机构：

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

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 79卷 / 21期

关键词：

ENANTIOSELECTIVE CATALYTIC EPOXIDATION; CONJUGATED LINOLEIC-ACID; ASYMMETRIC EPOXIDATION; HYDROGEN-PEROXIDE; FATTY-ACIDS; OXIDATION; OLEFINS; LIPOXYGENASE; ALCOHOLS; COMPLEX;

D O I：

10.1021/jo501958d

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Methyltrioxorhenium (MTO) complexed with pyridine was shown to be a highly effective catalyst for the regioselective monoepoxidation of conjugated di- and trienes using 30% H2O2 at or below room temperature. The resultant allylic epoxides, and the triols derived from them, are versatile synthetic intermediates as well as substructures present in many bioactive natural products. The site of epoxidation was dependent upon olefin substitution, olefin geometry (Z vs E), and the presence of electron-withdrawing substituents on adjacent carbons. For 1-acyl(silyl)oxypenta-2,4-dienes, epoxidation of the distal olefin was generally favored in contrast to the adjacent regioselectivity characteristic of Sharpless, peracid, and other directed epoxidations of hydroxylated dienes.

引用

页码：10323 / 10333

页数：11

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