通过缺电子炔烃与N-羟基邻苯二甲酰亚胺的碱催化分子间反应立体选择性合成3-亚甲基异吲哚啉-1-酮。

Stereoselective synthesis of 3-methyleneisoindolin-1-ones via base-catalyzed intermolecular reactions of electron-deficient alkynes with N-hydroxyphthalimides.

作者信息

Chen Xin, Ge Fei-Fei, Lu Tao, Zhou Qing-Fa

机构信息

†School of Basic Sciences, China Pharmaceutical University, Nanjing, 210009, P. R. China.

‡State Key Laboratory of Natural Medicines, China Pharmaceutical University, Nanjing, 210009, P. R. China.

出版信息

J Org Chem. 2015 Mar 20;80(6):3295-301. doi: 10.1021/acs.joc.5b00002. Epub 2015 Mar 2.

DOI:10.1021/acs.joc.5b00002

PMID:25710323

Abstract

Highly stereoselective intermolecular reactions of electron-deficient alkynes with N-hydroxyphthalimides for efficient construction of N-unprotected 3-methyleneisoindolin-1-ones have been developed through base catalytic strategies. The reaction of alkynoates with N-hydroxyphthalimides catalyzed by Bu3P in DMF at 150 °C gave the corresponding 3-methyleneisoindolin-1-ones with a (Z)-configuration, while the reaction of alkynoates with N-hydroxyphthalimides catalyzed by K2CO3 in DMF at 60 °C gave the corresponding 3-methyleneisoindolin-1-ones with an (E)-configuration, and (Z)-3-methyleneisoindolin-1-ones were obtained when alkyne ketones reacted with N-hydroxyphthalimide.

摘要

通过碱催化策略，已开发出缺电子炔烃与N-羟基邻苯二甲酰亚胺的高度立体选择性分子间反应，用于高效构建N-未保护的3-亚甲基异吲哚啉-1-酮。在150°C下，由Bu3P催化的炔酸酯与N-羟基邻苯二甲酰亚胺在DMF中的反应生成具有(Z)-构型的相应3-亚甲基异吲哚啉-1-酮，而在60°C下，由K2CO3催化的炔酸酯与N-羟基邻苯二甲酰亚胺在DMF中的反应生成具有(E)-构型的相应3-亚甲基异吲哚啉-1-酮，当炔酮与N-羟基邻苯二甲酰亚胺反应时，得到(Z)-3-亚甲基异吲哚啉-1-酮。