4553-07-5Relevant articles and documents
-
Schmidt,Ried
, p. 2431 (1969)
-
Palladium(II)-catalyzed cross-coupling of diazo compounds and isocyanides to access ketenimines
Bi, Xihe,Liu, Zhaohong,Cao, Shanshan,Wu, Jiayi,Zanoni, Giuseppe,Sivaguru, Paramasivam
, p. 12881 - 12887 (2020/11/18)
Diazo compounds and isocyanides are reactive functionalities and valuable building blocks commonly utilized in organic synthesis. Their cross-coupling for the synthesis of useful isolable ketenimines remains an unsolved challenge in synthetic chemistry. Herein, we report a general method for the preparation of ketenimines via a palladium-catalyzed cross-coupling of easily accessible diazo compounds with isocyanides. The reaction benefits from the use of readily available starting materials, a wide substrate scope, high functional group tolerance, and a high yield in products, and the resultant ketenimines are amenable to further functionalization. Experimental findings and DFT calculations unambiguously corroborate the initial formation of a Pd(II)? isocyanide complex as the active catalytic species, which enables the cross-coupling reaction via a migratory insertion of Pd(II)? carbene into isocyanide, with evidence suggesting that the oxidation state of Pd(II) remains unchanged during the reaction.
AlCl3 catalyzed coupling of: N-benzylic sulfonamides with 2-substituted cyanoacetates through carbon-nitrogen bond cleavage
Hu, Chen,Hong, Gang,Qian, Xiaofei,Kim, Kwang Rim,Zhu, Xiaoyan,Wang, Limin
supporting information, p. 4984 - 4991 (2017/07/10)
A new cross-coupling reaction of N-benzylic sulfonamides with 2-substituted cyanoacetates for the synthesis of 2-substituted benzylbenzene was reported. In the presence of AlCl3, a broad range of N-benzylic sulfonamides reacted smoothly with 2-substituted cyanoacetates to afford structurally diverse benzylbenzenes in moderate to excellent yields. The conversion could be enlarged to gram-scale efficiently. The practicability of this approach was further manifested in the synthesis of a related bioactive agent with high anti-inflammatory activity.
