通过自由基中间体光催化生成π-烯丙基钛配合物
Photocatalytic Generation of π-Allyltitanium Complexes via Radical Intermediates.
作者信息
Li Fusheng, Lin Shuangjie, Chen Yuqing, Shi Caizhe, Yan Huaipu, Li Chenchen, Wu Chao, Lin Luqing, Duan Chunying, Shi Lei
机构信息
Dalian University of Technology, Zhang Dayu School of Chemistry, State Key Laboratory of Fine Chemicals, 116024, Dalian, China.
Frontier Institute of Science and Technology, Xi'an Jiaotong University, 710054, Xi'an, China.
出版信息
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1561-1566. doi: 10.1002/anie.202010780. Epub 2020 Nov 12.
The addition of π-allylmetal complexes to carbonyls is the most important route to homoallylic alcohols. This study reports the first photocatalytic generation of π-allyltitanium complexes by a radical strategy. This novel strategy enables the three-component allylation of carbonyls with 1,3-butadiene, providing rapid access to valuable homoallylic alcohols (over 60 examples). The exceptional regio- and diastereoselectivity provided by dual photoredox/Ti catalysis is comparable to that of the Cr-catalyzed Nozaki-Hiyama-Kishi allylation reaction.
向羰基化合物中添加π-烯丙基金属配合物是制备高烯丙醇的最重要途径。本研究报道了通过自由基策略首次光催化生成π-烯丙基钛配合物。这种新策略实现了羰基化合物与1,3-丁二烯的三组分烯丙基化反应，能够快速合成有价值的高烯丙醇（超过60个实例）。双光氧化还原/钛催化提供的优异区域和非对映选择性与铬催化的野崎-桧山-岸烯丙基化反应相当。
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