八羰基二钴介导的环氧醇的内型环化反应：2-乙炔基-3-羟基-2-甲基四氢吡喃和2-乙炔基-3-羟基-3-甲基四氢吡喃衍生物的合成

Co2(CO)8-mediated endo mode cyclization of epoxy-alcohol: synthesis of 2-ethynyl-3-hydroxy-2-methyltetrahydropyran and 2-ethynyl-3-hydroxy-3-methyltetrahydropyran derivatives.

作者信息

Mukai C, Yamaguchi S, Kim I J, Hanaoka M

机构信息

Faculty of Pharmaceutical Sciences, Kanazawa University, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2001 May;49(5):613-8. doi: 10.1248/cpb.49.613.

DOI:10.1248/cpb.49.613

PMID:11383616

Abstract

Successive treatment of 4,5-epoxy-5-methyl-7-trimethylsilyl-6-heptyne-1-ol with Co2(CO)8 at 0 degrees C and a catalytic amount of BF3 x OEt2 at -78 degrees C gave the tetrahydropyran derivatives with the cobalt-complexed moiety. Similarly 4,5-epoxy-4-methyl-7-trimethylsilyl-6-heptyne-1-ol underwent ring closure under the above conditions to provide the corresponding tetrahydropyran derivatives. The preferential endo mode cyclization over the exo one was observed in these experiments.

摘要

在0℃下用Co2(CO)8以及在-78℃下用催化量的BF3·OEt2对4,5-环氧-5-甲基-7-三甲基硅基-6-庚炔-1-醇进行连续处理，得到了带有钴络合部分的四氢吡喃衍生物。类似地，4,5-环氧-4-甲基-7-三甲基硅基-6-庚炔-1-醇在上述条件下发生闭环反应，生成相应的四氢吡喃衍生物。在这些实验中观察到了内型环化比外型环化更具优势。