铑催化的 CX 试剂对烯烃的对映选择性自由基加成反应。
Rhodium-Catalyzed Enantioselective Radical Addition of CX Reagents to Olefins.
机构信息
Department of Biochemistry, UT Southwestern Medical Center, 5323 Harry Hines Blvd, Dallas, TX, 75390-9038, USA.
Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, 15260, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Jul 17;56(30):8780-8784. doi: 10.1002/anie.201704074. Epub 2017 Jun 14.
Abstract
We describe the synthetically useful enantioselective addition of Br-CX (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)Rh BrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.
摘要
我们描述了 Br-CX（X=Cl 或 Br）与末端烯烃的对映选择性加成反应，该反应可用于引入三卤甲基基团并生成光学活性的仲溴化物。计算和实验证据支持不对称原子转移自由基加成（ATRA）机理，其中立体决定步骤涉及苄基自由基中间体从[(双膦）Rh BrCl]配合物中进行的外球溴原子的提取。这种机理在不对称催化中似乎是前所未有的。
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