芳香β-和γ-亚氨基酯的电还原分子内偶联：一种合成N-烷氧羰基-2-芳基-3-酮以及吡咯烷和哌啶的顺式-2-芳基-3-醇的新方法。

Electroreductive intramolecular coupling of aromatic beta- and gamma-imino esters: a new synthetic method for N-alkoxycarbonyl-2-aryl-3-ones and cis-2-aryl-3-ols of pyrrolidines and piperidines.

作者信息

Kise Naoki, Ohya Kengo, Arimoto Kie, Yamashita Yutaka, Hirano Yuuki, Ono Tadahiro, Ueda Nasuo

机构信息

Department of Biotechnology, Faculty of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan.

出版信息

J Org Chem. 2004 Oct 29;69(22):7710-9. doi: 10.1021/jo0488917.

DOI:10.1021/jo0488917

PMID:15498001

Abstract

The electroreduction of aromatic beta- and gamma-imino esters prepared from beta-alanine and GABA in the presence of chlorotrimethylsilane and subsequent N-alkoxycarbonylation of the resulting five- and six-membered cyclized amines gave mixed ketals of N-alkoxycarbonyl-2-arylpyrrolidin-3-ones and 2-arylpiperidin-3-ones, respectively. The best result of the electroreductive intramolecular coupling was achieved using Bu(4)NClO(4) as a supporting electrolyte and a Pb cathode in THF. Acid hydrolysis of the mixed ketals afforded N-alkoxycarbonyl-2-arylpyrrolidin-3-ones and 2-arylpiperidin-3-ones in good yields. The reduction of these ketones with NaBH(4) in methanol afforded the corresponding N-alkoxycarbonyl-cis-2-arylpyrrolidin-3-ols and cis-2-arylpiperidin-3-ols diastereospecifically.

摘要

由β-丙氨酸和γ-氨基丁酸制备的芳香β-和γ-亚氨基酯在三甲基氯硅烷存在下进行电还原，随后对所得的五元及六元环化胺进行N-烷氧基羰基化反应，分别得到了N-烷氧基羰基-2-芳基吡咯烷-3-酮和2-芳基哌啶-3-酮的混合缩酮。使用四丁基高氯酸铵作为支持电解质和在四氢呋喃中使用铅阴极，实现了电还原分子内偶联的最佳结果。混合缩酮的酸水解以良好的产率得到了N-烷氧基羰基-2-芳基吡咯烷-3-酮和2-芳基哌啶-3-酮。在甲醇中用硼氢化钠还原这些酮，非对映选择性地得到了相应的N-烷氧基羰基-顺式-2-芳基吡咯烷-3-醇和顺式-2-芳基哌啶-3-醇。