文献类型：期刊文献

英文题名：Chemo- and Regioselective Organo-Photoredox Catalyzed Hydroformylation of Styrenes via a Radical Pathway

作者：Huang, He[1];Yu, Chenguang[1];Zhang, Yueteng[1];Zhang, Yongqiang[2,3];Mariano, Patrick S.[1];Wang, Wei[1,2,3]

机构：[1]Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA;[2]East China Univ Sci & Technol, Sch Pharm, State Key Lab Bioengn Reactor, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Sch Pharm, Shanghai Key Lab New Drug Design, Shanghai 200237, Peoples R China

年份：2017

卷号：139

期号：29

起止页码：9799

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20173104001096);WOS:【SCI-EXPANDED(收录号:WOS:000406649600013)，CCR-EXPANDED(收录号:WOS:000406649600013)】；

基金：Financial support for this work provided by the NSF (CHE-1565085, W.W.), the ACS-PRF (57164-ND1, W.W.), and the National Natural Science Foundation of China (21572055 and 21372073, W.W.) is gratefully acknowledged.

语种：英文

外文关键词：Carboxylation - Catalysis - Regioselectivity - Hydroformylation - Free radicals - Styrene

摘要：An unprecedented, chemo- and regioselective, organo-photoredox catalyzed hydroformylation reaction of aryl olefins with diethoxyacetic acid as the formylation reagent is described. In contrast to traditional transition metal promoted ionic hydroformylation reactions, the new process follows a unique photoredox promoted, free radical pathway. In this process, a formyl radical equivalent, produced from diethoxacetic acid through a dye (4CzIPN) photocatalyzed, sequential oxidation decarboxylation route, regio- and chemoseleclively adds to a styrene substrate. Importantly, under the optimized reaction conditions the benzylic radical formed in this manner is reduced by SET from the anion radical of 4CzIPN to generate a benzylic anion. Finally, protonation produces the hydroformylation product. By using the new protocol, aldehydes can be generated regioselectively in up to 90% yield. A broad array of functional groups is tolerated in the process, which takes place under mild, metal-free conditions.