The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest.Herein,the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene sp...The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest.Herein,the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene species(I),which is derived from Rh_(2)(ll)-catalyzed denitrogenation of 3-diazoindolin-2-imines,to produce synthetically useful 2-iminoindolin-nitrones is described.Mechanistically,the N-attack of nitrosoarenes with the carbene site of I is proposed.For the analogous Rh_(2)(ll)-catalyzed reaction of nitrosoarenes with N-sulfonyl-1,2,3-triazoles reported by Li and co-workers(Org.Lett.2014,16,6394),however,the O-attack of nitrosoarenes with the carbene site of α-imino rhodium carbene species(II)is more favorable to occur than the N-attack.The subsequent transformation to yield the product of N-acylamidines is rationalized based on computational studies.The mechanistic differ-ences for the reactions of nitrosoarenes with a-imino rhodium carbene species I and II are discussed.展开更多
基金the National Natural Science Foundation of China(No.21973068)the Project of Scientific and Technologic Infrastructure of Suzhou(No.SZS201708)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)for financial support.
文摘The employment of α-iminometallocarbenes to construct valuable N-containing compounds has attracted significant research interest.Herein,the nucleophilic addition of nitrosoarenes with the α-imino rhodium carbene species(I),which is derived from Rh_(2)(ll)-catalyzed denitrogenation of 3-diazoindolin-2-imines,to produce synthetically useful 2-iminoindolin-nitrones is described.Mechanistically,the N-attack of nitrosoarenes with the carbene site of I is proposed.For the analogous Rh_(2)(ll)-catalyzed reaction of nitrosoarenes with N-sulfonyl-1,2,3-triazoles reported by Li and co-workers(Org.Lett.2014,16,6394),however,the O-attack of nitrosoarenes with the carbene site of α-imino rhodium carbene species(II)is more favorable to occur than the N-attack.The subsequent transformation to yield the product of N-acylamidines is rationalized based on computational studies.The mechanistic differ-ences for the reactions of nitrosoarenes with a-imino rhodium carbene species I and II are discussed.
