（S）-（-）-（E）-15,16-二氢明喹炔酸的全合成：一种高效抗癌剂。

Total synthesis of (S)-(-)-(E)-15,16-dihydrominquartynoic acid: a highly potent anticancer agent.

作者信息

Gung Benjamin W, Kumi Godwin

机构信息

Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, USA.

出版信息

J Org Chem. 2004 May 14;69(10):3488-92. doi: 10.1021/jo049920g.

DOI:10.1021/jo049920g

PMID:15132560

Abstract

The conjugated entriyne natural product, (S)-(E)-15,16-dihydrominquartynoic acid (1), is synthesized in five linear steps and 30% overall yield from the known aldehyde 11. The key step is a one-pot in situ desilylation/Cadiot-Chodkiewicz coupling reaction affording the entriyne unit. The bromoalkyne 6 with an omega-carboxylic acid group was found to undergo a copper-catalyzed cross-coupling reaction producing the desired diyne intermediate 10, while the corresponding omega-ester bromoalkyne 14 failed to couple with triethylsilylacetylene under a variety of conditions.

摘要

共轭烯炔天然产物（S）-（E）-15,16-二氢米喹炔酸（1）以已知醛11为原料，经五步线性反应合成，总收率为30%。关键步骤是一锅法原位脱硅/Cadiot-Chodkiewicz偶联反应，得到烯炔单元。发现带有ω-羧酸基团的溴代炔烃6能发生铜催化的交叉偶联反应，生成所需的二炔中间体10，而相应的ω-酯溴代炔烃14在各种条件下都不能与三乙基硅基乙炔偶联。