TOTAL SYNTHESIS OF (+)-4-OXO-5,6,9,10-TETRADEHYDRO-4,5-SECOFURANOEREMOPHILANE-5,1-CARBOLACTONE VIA NOVEL LACTONE CONSTRUCTION THROUGH ALLENE INTRAMOLECULAR CYCLO-ADDITION

被引：43

作者：

HAYAKAWA, K ^{[1
]}

NAGATSUGI, F ^{[1
]}

KANEMATSU, K ^{[1
]}

机构：

[1] KYUSHU UNIV 62, FAC PHARMACEUT SCI, INST SYNTHET ORGAN CHEM, HIGASHI KU, FUKUOKA 812, JAPAN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1988年 / 53卷 / 04期

关键词：

D O I：

10.1021/jo00239a033

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The first asymmetric synthesis of the title compound 1 is described. The crucial step is a facile construction of the tricyclic lactone, the basic skeleton of 1, via allene intramolecular cycloaddition. Methyl (R)-(-)-3-hydroxyhept-6-enoate (3) was converted into the (R)-propargyl ether 8 in six steps. Base treatment (t-BuOK/t-BuOH,83.degree.C) of 8 caused a smooth cyclization via the intramolecular Diels-Alder reaction of the allenyl ether intermediate to give 9, which on successive hydration and oxidation provided the lactone 10 as a mixture of diastereomers. Aromatization of 10 afforded a single product (11), which was subjected to the Wacker oxidation to give (R)-(+)-1.

引用

页码：860 / 863

页数：4

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