351-22-4Relevant articles and documents
Ni-Catalyzed Iterative Alkyl Transfer from Nitrogen Enabled by the in Situ Methylation of Tertiary Amines
Nwachukwu, Chideraa Iheanyi,McFadden, Timothy Patrick,Roberts, Andrew George
, p. 9979 - 9992 (2020/09/03)
Current methods to achieve transition-metal-catalyzed alkyl carbon-nitrogen (C-N) bond cleavage require the preformation of ammonium, pyridinium, or sulfonamide derivatives from the corresponding alkyl amines. These activated substrates permit C-N bond cleavage, and their resultant intermediates can be intercepted to affect carbon-carbon bond-forming transforms. Here, we report the combination of in situ amine methylation and Ni-catalyzed benzalkyl C-N bond cleavage under reductive conditions. This method permits iterative alkyl group transfer from tertiary amines and demonstrates a deaminative strategy for the construction of Csp3-Csp3 bonds. We demonstrate PO(OMe)3 (trimethylphosphate) to be a Ni-compatible methylation reagent for the in situ conversion of trialkyl amines into tetraalkylammonium salts. Single, double, and triple benzalkyl group transfers can all be achieved from the appropriately substituted tertiary amines. Transformations developed herein proceed via recurring events: The in situ methylation of tertiary amines by PO(OMe)3, Ni-catalyzed C-N bond cleavage, and concurrent Csp3-Csp3 bond formation.
Reductive Homocoupling of Organohalides Using Nickel(II) Chloride and Samarium Metal
Liu, Yongjun,Xiao, Shuhuan,Qi, Yan,Du, Feng
, p. 673 - 678 (2017/03/22)
A homocoupling method for organohalides and organosulfonates promoted by samarium metal and HMPA, and catalyzed by NiCl2 has been developed. Various organohalides (benzyl, aryl, heterocyclic, alkenyl and alkyl halides), α-haloacetophenones, and phenyl organosulfonates were tolerated, and the reaction afforded coupling products with high efficiency. Excellent chemoselectivity was exhibited between halides and other groups, such as ?COOH, ?NO2, halogen, heterocyclic ring, ester, and ketone groups. The stereoselectivity suggested that the reaction mechanism might involve an organosamarium species.
An unprecedented oxidative intermolecular homo coupling reaction between two sp3C–sp3C centers under metal-free condition
Sahoo, Santosh K.
supporting information, p. 3476 - 3480 (2016/07/15)
An unprecedented formation of benzylic sp3C–sp3C coupled dibenzylic products has been illustrated. The reactions have been carried out in the presence of three oxidizing reagents, i.e., diacetoxy-iodobenzene (IBDA), N-fluorobenzenesulfonimide (NFSI), and pyridine (Py) using toluene derivatives.