Ni-Catalyzed Reductive Dibenzylation of Trifluoromethylalkenes for CF₃-Containing All-Carbon Quaternary Center Construction

Abstract

A Ni-catalyzed reductive dicarbofunctionalization of α-CF 3 styrenes with benzyl bromides has been accomplished. This transformation obviates the commonly facile β-F elimination effectively and enables the creation of CF 3 -substituted all-carbon quaternary centers of pharmaceutical interests. Preliminary mechanistic studies suggest a pathway consisting of benzyl radical addition and subsequent nickelmediated benzylation of the resulting α-CF 3 -embedded tertiary C radical.

Iron-Mediated Dialkylation of Alkenylarenes with Benzyl Bromides

“…There are two known reports of dibenzylation of vinyl arenes in the literature: the first, by Cheng and co-workers, relies on the use of benzylated Hantzsch esters, which must be prepared prior to reaction, and it also requires a noble metal iridium catalyst (Scheme a) . The second precedent comes from Feng and co-workers who report the dibenzylation of α-CF 3 styrenes using a method which involves stoichiometric manganese as a reductant, plus the use of a ligand with a nickel catalyst (Scheme b) . Herein, we disclose a new method for the dibenzylation of vinyl arenes using iron powder in conjunction with benzyl bromides.…”

Copper-Catalyzed Synthesis of 4-CF3-1,2,3-Triazoles: An Efficient and Facile Approach via Click Reaction

“…Since the time of its discovery in strategies to optimize the pharmacological properties of drug candidates [ 1 , 2 , 3 , 4 ], incorporation of the trifluoromethyl group has become a promising approach to discover new and/or improve existing bioactive compounds [ 5 , 6 , 7 , 8 ]. Although several valuable methods have been developed for the synthesis of trifluoromethyl-substituted compounds [ 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ], methods that incorporate this group in an efficient and regiospecific manner remain in high demand [ 21 , 22 , 23 , 24 , 25 , 26 , 27 ], especially in the case of heterocyclic compounds [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 ].…”