Acid-Promoted Rearrangement of Drimane Type Epoxy Compounds and Their Application in Natural Product Synthesis

被引：8

作者：

Fujiwara, Naoko ^{[3
]}

Kinoshita, Masako ^{[1
]}

Uchida, Akira ^{[2
]}

Ono, Machiko ^{[3
]}

Kato, Keisuke ^{[1
]}

Akita, Hiroyuki ^{[1
]}

机构：

[1] Toho Univ, Fac Pharmaceut Sci, Chiba 2748510, Japan

[2] Toho Univ, Fac Sci, Chiba 2748510, Japan

[3] Int Univ Hlth & Welf, Sch Pharmaceut Sci, Ohtawara, Tochigi 3248501, Japan

来源：

CHEMICAL & PHARMACEUTICAL BULLETIN | 2012年 / 60卷 / 04期

关键词：

alpha-epoxy drimenol; alpha-epoxy bicyclofarnesol; alpha-epoxy drimenyl cyanide; (10S; 7R)-7-acetoxy-labda-8(17); 13(14)E-dien-15-ol; (9S)-austrodoric acid; acid-promoted rearrangement;

D O I：

10.1248/cpb.60.562

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

The reactions of (+/-)-alpha-epoxy drimenol (4) and (+/-)-alpha-epoxy drimenyl cyanide (6) with acids (proton acid or Lewis acid) selectively gave the rearranged aldehyde (+/-)-13 and (+/-)-15 having the hydroindane skeleton, respectively, while the reactions of (+/-)-4 and (+/-)-6 with Dibal-H selectively afforded the allyl alcohol (+/-)-14 and (+/-)-16, respectively. The reactions of (8aR)-6 and (8aS)-6 with Dibal-H were applied for the determination of the absolute structure of natural 7 beta-acetoxy-ent-labda-8(17),13(14)E-dien-15-ol (18). The reaction of (+/-)-alpha-epoxy bicyclofarnesol (5) and (8aS)-5 with proton acid selectively provided the rearranged ketol (+/-)- and (8aS)-31 having the hydroindane skeleton, respectively. The optically active (8aS)-31 was converted to the natural (9S)-austrodoric acid (33).

引用

页码：562 / 570

页数：9

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