We demonstrate that a bulky cyclic amino ligand,specifically 1,1,3,3-tetraphenylisoindolinyl,can facilitate the formation of a transient stannyne,endowed with adjacent ambiphilic carbon and tin centers.This stannyne,m...We demonstrate that a bulky cyclic amino ligand,specifically 1,1,3,3-tetraphenylisoindolinyl,can facilitate the formation of a transient stannyne,endowed with adjacent ambiphilic carbon and tin centers.This stannyne,manifesting carbene-like behavior,engages in an unprecedented sequence of reactions,including Buchner ring expansion,[1,3]sigmatropic,and[1,5]-sigmatropic shifts,culminating in the synthesis of a stable cyclic(alkyl)(amino)stannylene.This compound represents the first tin analogue of the well-known cyclic(alkyl)(amino)carbenes.Both the bonding configuration and the formation process of this stannylene are thoroughly analyzed through quantum chemical computations.Our findings pave the way for further synthesis of unusual main group species using bulky isoindolinyl substituents,emphasizing their potential as a versatile tool in synthetic chemistry.展开更多
基金supported by the National Natural Science Foundation of China(22350004,22101114,22271132)the ShenzhenScienceandTechnologyInnovationProgram(20231120110042001)+1 种基金the High Level of Special Funds(G03050K003)the Guangdong Innovation and Entrepreneurial Research Team Program(2021ZT09C278)。
文摘We demonstrate that a bulky cyclic amino ligand,specifically 1,1,3,3-tetraphenylisoindolinyl,can facilitate the formation of a transient stannyne,endowed with adjacent ambiphilic carbon and tin centers.This stannyne,manifesting carbene-like behavior,engages in an unprecedented sequence of reactions,including Buchner ring expansion,[1,3]sigmatropic,and[1,5]-sigmatropic shifts,culminating in the synthesis of a stable cyclic(alkyl)(amino)stannylene.This compound represents the first tin analogue of the well-known cyclic(alkyl)(amino)carbenes.Both the bonding configuration and the formation process of this stannylene are thoroughly analyzed through quantum chemical computations.Our findings pave the way for further synthesis of unusual main group species using bulky isoindolinyl substituents,emphasizing their potential as a versatile tool in synthetic chemistry.
