Yoshinaga Yukako, Yamamoto Takeshi, Suginome Michinori
Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto, 615-8510, Japan.
Angew Chem Int Ed Engl. 2020 Apr 27;59(18):7251-7255. doi: 10.1002/anie.201914864. Epub 2020 Mar 10.
Enantiospecific intramolecular Suzuki-Miyaura-type coupling with α-(2-halobenzoylamino)benzylboronic esters to give 3-substituted isoindolinones is achieved by using copper catalysts with 2,2'-bipyridine-based achiral ligands. Enantioenriched α-aminobenzylboron reactants bearing a hydrogen atom at the boron-bound stereogenic carbons undergo stereoinvertive coupling in the presence of a 6-phenyl-2,2'-bipyridine ligand with high enantiospecificity. α-Aminobenzylboronates bearing fully substituted boron-bound stereogenic centers also gave the 3,3-disubstituted isoindolinones with stereospecific stereochemical inversion in the presence of simple 2,2'-bipyridine as a ligand.
通过使用带有基于2,2'-联吡啶的非手性配体的铜催化剂，实现了α-(2-卤代苯甲酰氨基)苄基硼酸酯的对映体特异性分子内铃木-宫浦型偶联反应，生成3-取代异吲哚啉酮。在硼连接的手性碳上带有氢原子的对映体富集的α-氨基苄基硼反应物，在6-苯基-2,2'-联吡啶配体存在下进行立体反转偶联反应，具有高对映体特异性。在简单的2,2'-联吡啶作为配体存在下，带有完全取代的硼连接手性中心的α-氨基硼酸苄酯也能以立体特异性的立体化学反转生成3,3-二取代异吲哚啉酮。
