Photoinitiated ambient temperature copper-catalyzed atom transfer radical addition (ATRA) and cyclization (ATRC) reactions in the presence of free-radical diazo initiator (AIBN)

被引：37

作者：

Balili, Marielle Nicole C. ^{[1
]}

Pintauer, Tomislav ^{[1
]}

机构：

[1] Duquesne Univ, Dept Chem & Biochem, Pittsburgh, PA 15282 USA

来源：

DALTON TRANSACTIONS | 2011年 / 40卷 / 12期

基金：

美国国家科学基金会;

关键词：

ORGANIC-SYNTHESIS; REDUCING AGENTS; KHARASCH ADDITION; CHAIN REACTIONS; POLYMERIZATION; COMPLEXES; DESIGN; TRIS(2-PYRIDYLMETHYL)AMINE; PRECURSOR;

D O I：

10.1039/c0dt01764g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The use of UV light in copper-catalyzed atom transfer radical addition (ATRA) and cyclization (ATRC) reactions of various (poly) halogenated compounds to highly active alkenes in the presence of AIBN is reported. Radicals generated from photodecomposition of AIBN efficiently regenerated the copper(I) complex at ambient temperature enabling ATRA of CCl4 and CBr4 with catalyst loadings as low as 0.05 mol-%. The desired monoadduct was obtained in lower yields in the ATRA of less active halogenated compounds, which was mostly due to incomplete alkene conversions. Ambient temperature ATRA of CCl4 to various 1,6-dienes followed by sequential ATRC was also performed in the presence of UV light using [Cu-II(TPMA)Cl][Cl] complex and AIBN. High yields of the 5-exo-trig cyclic product were obtained for all dienes with preferential formation of the cis isomer.

引用

页码：3060 / 3066

页数：7

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