Cu-Catalyzed Remote Transarylation of Amines via Unstrained C–C Functionalization

Abstract

Remote arylation of amines via C−C bond functionalization has not been reported yet. Herein, we develop the γ-transarylation of amines through the cleavage of unstrained C−C bond enabled by copper catalysis under mild conditions, representing the example of utilization of unstrained C−C bond for metal-catalyzed C−C cross-coupling. Mechanistic investigations reveal that the redox-neutral reaction undergoes an intercepted radical pathway to cleave the C sp 2 −C sp 3 bond, followed by the combination with copper-catalyzed arylation reaction in the presence of aryl boronic acid to construct a new C sp 2 −C sp 3 bond.

Rapid access to t-butylalkylated olefins enabled by Ni-catalyzed intermolecular regio- and trans-selective cross-electrophile t-butylalkylation of alkynes

“…To this end, the use of two distinct alkyl electrophiles to sequentially couple across alkynes under reductive conditions renders an appealing alternative to access multialkylated olefins with defined stereochemistry. 18 As our continuous interest in earth-abundant metal-catalyzed reductive selective transformations, 19 we herein report the Ni-catalyzed radical addition of one alkyl bromide onto alkynes, followed by a Ni-catalyzed coupling with another alkyl halide to afford the dialkylation of alkynes with exquisite trans -selectivity under reductive conditions ( Scheme 1d ). This three-component reaction enables the sequential installation of two distinct alkyl bromides onto alkynes, allowing for the regio- and diastereoselective dialkylation of alkynes without the use of organometallic reagents at room temperature.…”

Nitrogenation and Oxygenation of an Unstrained C–C Bond Enabled by the Merger of Visible-Light and Cu-Catalysis

“…Shi and co-workers reported a silver catalyzed remote aryl migration of triflic amides to construct a C–O bond under oxidative conditions . Despite these advances, a general method merging radical activation of an unstrained C–C bond with the metal-catalyzed cross-coupling process to construct carbon–nitrogen and carbon–oxygen bonds remains unknown. , Here, we report the successful realization of site-selective azidation and etherification of an unstrained C–C bond via an aryl migration strategy under visible-light and copper catalysis (Scheme d). This method operates under mild and redox-neutral conditions that allow for the consecutive cleavage of an inert γ-C–C bond of amines and reconstruction of new carbon–heteroatom bonds, providing a powerful tool for unstrained carbon–carbon bond utilization as metal-catalzyed cross-coupling precursors.…”