Butenolide annelation using a manganese(III) oxidation. A synthesis of chromolaenin (Laevigatin)

被引：10

作者：

Demir, AS ^{[1
]}

Gercek, Z ^{[1
]}

Duygu, N ^{[1
]}

Igdir, AC ^{[1
]}

Reis, O ^{[1
]}

机构：

[1] Middle E Tech Univ, Dept Chem, TR-06531 Ankara, Turkey

来源：

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1999年 / 77卷 / 08期

关键词：

chromolaenin (Laevigatin); manganese(III) acetate oxidation; aromatic ketones; butenolide annelation; lactone; Horner-Watsworth-Emmons cyclization; Arbuzov reaction;

D O I：

10.1139/cjc-77-8-1336

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A procedure was developed for the annelation of a butenolide to an aromatic ketone that highlighted a manganese(III) oxidation of an aromatic ketone. The merit of this procedure was illustrated in a synthesis of Chromolaenin (Laevigatin) (1) from 4,7-dimethyl-1-tetralone (2c). Oxidation of tetralone and indanone with manganese(III) acetate in the presence of chloro- or bromopropionic acid or their Mn(II) salts furnished a alpha-haloesters 3a-d. An Arbuzov reaction of haloesters with triethylphosphite and an intramolecular Horner-Watsworth-Emmons cyclization of the resulting phosphonate gave butenolide 5a, b in 77-79% yield. This methodology was also applied to 4,7-dimethyl-1-tetralone (2c), and the corresponding butenolide 6 is synthesized in 85% yield, which was then converted to Chromolaenin (1) using DIBAL-H.

引用

页码：1336 / 1339

页数：4