光学活性5-烷氧基-6-甲基环己-2-烯-1-酮和4-烷氧基-5-甲基环戊-1-烯基苯甲酸酯的合成。

Synthesis of optically active 5-alkoxy-6-methylcyclohex-2-en-1-ones and 4-alkoxy-5-methylcyclopent-1-enyl benzoate.

作者信息

Turks Maris, Vogel Pierre

机构信息

Laboratory of Glycochemistry and Asymmetric Synthesis, Swiss Federal Institute of Technology (EPFL), Batochime, CH-1015 Lausanne, Switzerland.

出版信息

J Org Chem. 2009 Jan 2;74(1):435-7. doi: 10.1021/jo801981c.

DOI:10.1021/jo801981c

PMID:19012433

Abstract

The reaction of (-)-(1E,3Z)-2-methyl-1-((1S)-1-phenylethoxy)penta-1,3-dien-3-ol benzoate with allyltrimethylsilane in SO2 and in the presence of a catalytic amount of Tf2NTMS gives a silyl sulfinate intermediate that furnishes (-)-(6Z,1'S,4S,5S)-5-methyl-4-(1'-phenylethoxy)octa-1,6-dien-6-yl benzoate after acidic workup. The latter undergoes ring-closing metathesis producing (-)-(2S,3S)-2-methyl-3-((1S)-1-phenylethoxy)cyclopent-5-en-1-yl benzoate. It has been converted also into the corresponding trimethylsilyl enol ether. After oxidation, an enone is obtained that undergoes ring-closing metathesis giving (-)-(5S,6S)-6-methyl-5-((1S)-1-phenylethoxy)cyclohex-2-en-1-one.

摘要

(-)-(1E,3Z)-2-甲基-1-((1S)-1-苯乙氧基)戊-1,3-二烯-3-醇苯甲酸酯与烯丙基三甲基硅烷在二氧化硫中，在催化量的双(三氟甲磺酰)亚胺三甲基硅酯存在下反应，生成一种亚磺酰硅中间体，经酸性后处理得到(-)-(6Z,1'S,4S,5S)-5-甲基-4-(1'-苯乙氧基)辛-1,6-二烯-6-基苯甲酸酯。后者进行闭环复分解反应生成(-)-(2S,3S)-2-甲基-3-((1S)-1-苯乙氧基)环戊-5-烯-1-基苯甲酸酯。它也已被转化为相应的三甲基硅烯醇醚。氧化后，得到一种烯酮，该烯酮进行闭环复分解反应生成(-)-(5S,6S)-6-甲基-5-((1S)-1-苯乙氧基)环己-2-烯-1-酮。