Biomimetic rearrangements of simplified labdane diterpenoids

被引：36

作者：

George, Jonathan H. ^{[1
]}

McArdle, Mark ^{[1
]}

Baldwin, Jack E. ^{[1
]}

Adlington, Robert M. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Chem Res Lab, Oxford OX1 3TA, England

来源：

TETRAHEDRON | 2010年 / 66卷 / 33期

关键词：

Biomimetic synthesis; Labdanes; Clerodanes; CARBONYL-COMPOUNDS; MARINE SPONGE; METHYLENATION; BIOSYNTHESIS;

D O I：

10.1016/j.tet.2010.05.052

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Simplified ethyl-substituted labdane diterpenoids 14 and 19 have been synthesised from (+)-sclareolide (18). Biomimetic rearrangements of these compounds, involving stereospecific 1,2-alkyl and hydride shifts, have been carried out by treatment with a variety of Lewis and protic acids. Halimane compounds, such as 34 and simple dehydration products such as 3, 32 and 33 have been formed either selectively or as mixtures depending on the reaction conditions. However, further rearrangement to clerodane products such as 1 and 2 was not observed, indicating a high degree of enzymatic control for the in vivo formation of these natural products. (C) 2010 Elsevier Ltd. All rights reserved.

引用

页码：6321 / 6330

页数：10

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