A cycloaddition approach to tricyclic taxoid skeletons

被引:27
作者
Lu, YF [1 ]
Fallis, AG [1 ]
机构
[1] UNIV OTTAWA,DEPT CHEM,OTTAWA CARLETON CHEM INST,OTTAWA,ON K1N 6N5,CANADA
来源
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1995年 / 73卷 / 12期
关键词
Taxol(R); Diels-Alder; synthesis; diterpene; alkaloid;
D O I
10.1139/v95-278
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A cycloaddition approach to the functionalized tricyclo[9.3.1.0(3,8)]pentadecene skeleton contained in Taxol(R) is described. The cyclohexenone 13 was converted as illustrated to the nitrile-aldehyde 24 to which the diene and acetylenic side chains were attached by sequential nucleophilic additions. Removal of the trimethylsilyl protecting group and Dess-Martin oxidation afforded the triene 35. Microwave-assisted thermal cyclization stereoselectively generated the tricyclic ketone 36 whose structure was further established by conversion to the aromatic system 37 upon treatment with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). An epoxidation sequence was developed to introduce the epimeric C13 alcohol 47 as required for this cycloaddition strategy. Alternatively, an allylic oxidation (CrO3, 3,5-dimethylpyrazole) afforded the C13 ketone 49.
引用
收藏
页码:2239 / 2252
页数:14
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