Kainz Quirin M, Matier Carson D, Bartoszewicz Agnieszka, Zultanski Susan L, Peters Jonas C, Fu Gregory C
Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, CA 91125, USA.
Science. 2016 Feb 12;351(6274):681-4. doi: 10.1126/science.aad8313.
Despite a well-developed and growing body of work in copper catalysis, the potential of copper to serve as a photocatalyst remains underexplored. Here we describe a photoinduced copper-catalyzed method for coupling readily available racemic tertiary alkyl chloride electrophiles with amines to generate fully substituted stereocenters with high enantioselectivity. The reaction proceeds at -40°C under excitation by a blue light-emitting diode and benefits from the use of a single, Earth-abundant transition metal acting as both the photocatalyst and the source of asymmetric induction. An enantioconvergent mechanism transforms the racemic starting material into a single product enantiomer.
尽管铜催化领域已有大量成熟且不断发展的研究工作，但铜作为光催化剂的潜力仍未得到充分探索。在此，我们描述了一种光诱导铜催化的方法，该方法可使易于获得的外消旋叔烷基氯亲电试剂与胺发生偶联反应，以高对映选择性生成完全取代的立体中心。该反应在 -40°C 下由蓝色发光二极管激发进行，并受益于使用单一的、在地壳中储量丰富的过渡金属作为光催化剂和不对称诱导源。对映汇聚机理将外消旋起始原料转化为单一产物对映体。
