Ding Ransheng, De Los Santos Zeus A, Wolf Christian
Department of Chemistry, Georgetown University, 37th and O Streets, Washington, DC 20057, USA.
ACS Catal. 2019 Mar 1;9(3):2169-2176. doi: 10.1021/acscatal.8b05164. Epub 2019 Feb 6.
Diastereodivergent and enantioselective conversion of isatin ketimines to α-fluoro-β-aminonitriles with vicinal tetrasubstituted stereocenters is achieved by a chiral copper complex/guanidine base catalyzed Mannich reaction with proper choice of the bisphosphine ligand. The reaction is broad in scope, scalable, and provides efficient access to a series of 3-aminoindolinones exhibiting a quaternary carbon-fluorine stereocenter with high yields and stereoselectivities. Selective transformations of the Mannich reaction products into multifunctional 3-aminooxindoles without erosion of enantiomeric and diastereomeric purity highlight the synthetic utility.
通过手性铜络合物/胍碱催化的曼尼希反应，在适当选择双膦配体的情况下，实现了异吲哚酮酮亚胺向具有邻位四取代立体中心的α-氟-β-氨基腈的非对映发散和对映选择性转化。该反应适用范围广、可扩大规模，并能高效合成一系列具有季碳-氟立体中心的3-氨基吲哚酮，产率和立体选择性高。曼尼希反应产物选择性转化为多功能3-氨基氧化吲哚，且对映体和非对映体纯度不受影响，突出了其合成实用性。
