Stereoselective Synthesis of Highly Functionalized Indanes and Dibenzocycloheptadienes through Complex Radical Cascade Reactions

被引：148

作者：

Kong, Wangqing ^{[1
]}

Fuentes, Noelia ^{[1
]}

Garcia-Dominguez, Andres ^{[1
]}

Merino, Estibaliz ^{[1
]}

Nevado, Cristina ^{[1
]}

机构：

[1] Univ Zurich, Dept Chem, CH-8057 Zurich, Switzerland

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 08期

基金：

欧洲研究理事会; 瑞士国家科学基金会;

关键词：

alkene difunctionalization; aryl migration; dibenzocycloheptadienes; indanes; radical cascades; IPSO SUBSTITUTION-REACTIONS; METAL-FREE; UNACTIVATED ALKENES; BOND FORMATION; CATALYZED TRIFLUOROMETHYLATION; SMILES REARRANGEMENT; ASYMMETRIC-SYNTHESIS; ACTIVATED ALKENES; MOLECULAR-OXYGEN; ALLYLIC ALCOHOLS;

D O I：

10.1002/anie.201409659

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Two highly stereoselective radical-mediated syntheses of densely functionalized indanes and dibenzocycloheptadienes from ortho-vinyl- and ortho-vinylaryl-substituted N-(arylsulfonyl)-acrylamides, respectively, are presented here. The chemoselective addition of insitu generated radicals (X-.) onto the styrene moieties triggers an unprecedented reaction cascade, resulting in the formation of one new CX bond and two new CC bonds, a formal 1,4-aryl migration, and the extrusion of SO2 to generate an amidyl radical intermediate. This intermediate, upon Habstraction, leads to the observed 5- and 7-membered ring carbocyclic products, respectively, in a highly efficient manner.

引用

页码：2487 / 2491

页数：5

共 93 条

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