Multiple Wagner-Meerwein Shift. Biogenesis-like conversion of (±)-Δ7,8-Protoilludene to (±)-Hirsutene and related reactions
✍ Scribed by Kiyoharu Hayano; Yasufumi Ohfune; Haruhisa Shirahama; Takeshi Matsumoto
- Publisher
- John Wiley and Sons
- Year
- 1981
- Tongue
- German
- Weight
- 859 KB
- Volume
- 64
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
Abstract
Experimental details are given for the previous preliminary reports concerning conversion of protoilludane (28) to hirsutene (3) and related reactions. Treatment of each of the bicyclic analogs 9, 10, 12 and 13 of the former compound afforded a hirsutene analog 8, through multiple 1,2‐shift, together with other products. Treatment of a mixture of α‐ and β‐protoilludene ‐epoxides (29α and 29β) with BF~3~ · Et~2~O in hexane yielded hirsutane derivatives 30 and 32. Compound 30 in turn was converted to endo‐hirsutene 36, which had already been isomerized to hirsutene (3).