Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu, 610041, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2020 Jan 13;59(3):1176-1180. doi: 10.1002/anie.201912703. Epub 2019 Nov 28.
A cooperative Cu/Pd-catalyzed enantioselective synthesis of multisubstituted allenes is established. By employing chiral sulfoxide phosphine (SOP)/Cu and PdCl (dppf) complexes as catalysts, the 1,4-arylboration of 1,3-enynes provides an efficient approach to trisubstituted chiral allenes with up to 92 % yield and 97:3 er. Furthermore, by using 2-substituted 1,3-enynes as substrates, the tetrasubstituted chiral allenes were successfully generated using this strategy. Finally, theoretical calculations indicate that the transmetallation of the allenylcopper species is the rate-limiting step of this transformation.
建立了一种协同的 Cu/Pd 催化的对映选择性合成多取代丙二烯的方法。通过使用手性亚砜膦 (SOP)/Cu 和 PdCl(dppf) 配合物作为催化剂，1,3-炔烃的 1,4-芳基硼酸化提供了一种高效的方法，可得到高达 92%的产率和 97:3 的对映选择性的三取代手性丙二烯。此外，通过使用 2-取代的 1,3-炔烃作为底物，该策略成功地生成了四取代手性丙二烯。最后，理论计算表明，烯丙基铜物种的转金属化是该转化的速率限制步骤。
