笠贝聚丙酸酯的合成研究：卡隆德林B三氧杂金刚烷环系的合成与异构化

Synthetic studies on siphonariid polypropionates: synthesis and isomerization of the caloundrin B trioxaadamantane ring system.

作者信息

Beye Garrison E, Goodman Jonathan M, Ward Dale E

机构信息

Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon SK S7N 5C9, Canada.

出版信息

Org Lett. 2009 Mar 19;11(6):1373-6. doi: 10.1021/ol900192q.

DOI:10.1021/ol900192q

PMID:19281137

Abstract

(1R,3R,5R,7R,8S,9R,10S)-3,5-Diethyl-8,9,10-trimethyl-2,4,6-trioxatricyclo[3.3.1.1(3,7)]decan-1-ol (II), a model of the trioxaadamantane ring system embedded in caloundrin B, was prepared by isomerization of the thermodynamically unstable (9S)-diastereomer (I) in the presence of imidazole. Alternatively, isomerization of I with HF.py or DBU gave the hemiacetal III or its retro-Claisen ester IV, respectively, which represent structural motifs present in the closely related siphonariid polypropionates siphonarin B and baconipyrone C.

摘要

(1R,3R,5R,7R,8S,9R,10S)-3,5-二乙基-8,9,10-三甲基-2,4,6-三氧杂三环[3.3.1.1(3,7)]癸烷-1-醇（II）是嵌入卡隆德林B中的三氧杂金刚烷环系统的模型，它是通过在咪唑存在下使热力学不稳定的(9S)-非对映异构体（I）异构化制备的。另外，用HF·py或DBU使I异构化分别得到半缩醛III或其逆克莱森酯IV，它们代表了密切相关的笠贝多丙酸酯类西弗纳林B和培根尼吡喃酮C中存在的结构基序。