Non-bonding 1,5-S•••O interactions govern chemo- and enantioselectivity in isothiourea-catalyzed annulations of benzazoles

被引：122

作者：

Robinson, Emily R. T. ^{[1
]}

Walden, Daniel M. ^{[2
]}

Fallan, Charlene ^{[1
]}

Greenhalgh, Mark D. ^{[1
]}

Cheong, Paul Ha-Yeon ^{[2
]}

Smith, Andrew D. ^{[1
]}

机构：

[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland

[2] Oregon State Univ, Dept Chem, 135 Gilbert Hall, Corvallis, OR 97331 USA

来源：

CHEMICAL SCIENCE | 2016年 / 7卷 / 12期

基金：

欧洲研究理事会; 英国工程与自然科学研究理事会; 美国国家科学基金会;

关键词：

KINETIC RESOLUTION; DENSITY FUNCTIONALS; OXYGEN INTERACTIONS; BENZOTHIAZOLE; SULFUR; HOMOBENZOTETRAMISOLE; BENZOTETRAMISOLE; CYCLOADDITION; HETEROCYCLES; DERIVATIVES;

D O I：

10.1039/c6sc00940a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Isothiourea-catalyzed annulations between 2-acyl benzazoles and alpha, beta-unsaturated acyl ammonium intermediates are selectively tuned to form either lactam or lactone heterocycles in good yields (up to 95%) and high ee (up to 99%) using benzothiazole or benzoxazole derivatives, respectively. Computation gives insight into the significant role of two 1,5-S center dot center dot center dot O interactions in controlling the structural preorganization and chemoselectivity observed within the lactam synthesis with benzothiazoles as nucleophiles. When using benzazoles the absence of a second stabilizing non-bonding 1,5-S center dot center dot center dot O interaction leads to a dominant C-H center dot center dot center dot O interaction in determining structural preorganization and lactone formation.

引用

页码：6919 / 6927

页数：9

共 70 条

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