A chemoenzymatic synthesis of the linear triquinane (-)-hirsutene and identification of possible precursors to the naturally occurring (+)-enantiomer

被引:56
作者
Banwell, MG [1 ]
Edwards, AJ [1 ]
Harfoot, GJ [1 ]
Jolliffe, KA [1 ]
机构
[1] Australian Natl Univ, Res Sch Chem, Inst Adv Studies, Canberra, ACT 0200, Australia
关键词
chemoenzymatic; hirsutene; sesquiterpene; triquinane; oxadi-pi-methane; enantiodivergence; cycloaddition; cis-1,2-dihydrocatechol;
D O I
10.1016/j.tet.2003.10.122
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
An enantiomerically pure cis-1,2-dihydrocatechol, which is readily obtained via a toluene dioxygenase-mediated dihydroxylation of toluene in a whole-cell biotransformation process, has been converted over 17 steps into the linear triquinane (-)-hirsutene. Since the enantiomer of the starting material is also available this work constitutes a formal total synthesis of the naturally occurring (+)-form of hirsutene. Furthermore, minor modifications of the route used here offer the possibility of accessing (+)-hirsutene from the original starting material. (C) 2003 Elsevier Ltd. All rights reserved.
引用
收藏
页码:535 / 547
页数:13
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