A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR pr...A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR protocol lies in the utilization of chiral phosphoric acid-catalyzed triazane formation reaction with azodicarboxylates, which enables the enantioselective synthesis of various substituted indolines bearing C3-quaternary stereocenters with good to high enantioselectivities(with sfactors up to 70). Moreover, an intriguing parallel kinetic resolution(PKR) has been developed by combining triazane formation and dehydrogenation reactions using different azodicarboxylates. Experimental studies have provided insight into the mechanism of this PKR reaction, demonstrating stereoselectivity in both triazane formation and dehydrogenation steps, favoring the opposite enantiomers. The large-scale synthesis and diverse derivatizations of the products, particularly the imine groupcontaining 3H-indoles, demonstrate the value of these(P)KR methods.展开更多
A H_(4)SiW_(12)O_(40)-catalyzed three-component tandem reaction of 2-acylbenzoic acids,primary amines and phosphine oxides to form 3,3-disubstituted isoindolinones was developed.By employing A H_(4)SiW_(12)O_(40)as th...A H_(4)SiW_(12)O_(40)-catalyzed three-component tandem reaction of 2-acylbenzoic acids,primary amines and phosphine oxides to form 3,3-disubstituted isoindolinones was developed.By employing A H_(4)SiW_(12)O_(40)as the catalyst and dimethyl carbonate(DMC)as the solvent,a diverse range of 2-acylbenzoic acid derivatives and primary amines worked well to give the C3-phosphinoyl-functionalized 3,3-disubstituted isoindolinones with the yield range of 61%-87%.Advantages of this transformation include green catalyst and solvent,available starting materials,broad substrate scope,high efficiency and operational simplicity with water as the sole by-product.The strategy achieved an efficient and green molecular fragment assembly to access isoindolinones,which would provide opportunities for the synthesis of potential biologically active molecules in a green manner.展开更多
基金supported by the National Natural Science Foundation of China(22171186,22222107)ShanghaiTech University Start-up FundingAnalytical Instrumentation Center(#SPSTAIC10112914),SPST,ShanghaiTech University。
文摘A novel kinetic resolution(KR) method has been developed for 3,3-disubstituted indolines, whose catalytic asymmetric synthesis remains a significant challenge in organic synthesis. The key to the success of this KR protocol lies in the utilization of chiral phosphoric acid-catalyzed triazane formation reaction with azodicarboxylates, which enables the enantioselective synthesis of various substituted indolines bearing C3-quaternary stereocenters with good to high enantioselectivities(with sfactors up to 70). Moreover, an intriguing parallel kinetic resolution(PKR) has been developed by combining triazane formation and dehydrogenation reactions using different azodicarboxylates. Experimental studies have provided insight into the mechanism of this PKR reaction, demonstrating stereoselectivity in both triazane formation and dehydrogenation steps, favoring the opposite enantiomers. The large-scale synthesis and diverse derivatizations of the products, particularly the imine groupcontaining 3H-indoles, demonstrate the value of these(P)KR methods.
基金the National Natural Science Foundation of China(No.22001034)Jiangxi Provincial Natural Science Foundation(No.20212BAB213001).
文摘A H_(4)SiW_(12)O_(40)-catalyzed three-component tandem reaction of 2-acylbenzoic acids,primary amines and phosphine oxides to form 3,3-disubstituted isoindolinones was developed.By employing A H_(4)SiW_(12)O_(40)as the catalyst and dimethyl carbonate(DMC)as the solvent,a diverse range of 2-acylbenzoic acid derivatives and primary amines worked well to give the C3-phosphinoyl-functionalized 3,3-disubstituted isoindolinones with the yield range of 61%-87%.Advantages of this transformation include green catalyst and solvent,available starting materials,broad substrate scope,high efficiency and operational simplicity with water as the sole by-product.The strategy achieved an efficient and green molecular fragment assembly to access isoindolinones,which would provide opportunities for the synthesis of potential biologically active molecules in a green manner.