Methyl fluoroalkanoate as methyl-transferring reagent. Unexpected participation of BAl2 (SN2) mechanism in the reaction of methyl 2,3,3,3-tetrafluoro-2-methoxypropanoate with amines

In the reaction of methyl 2,3,3,3-tetrafluoro-2-methoxypropanoate with arylamines or arylmethylamines, an unexpected methyl transfer from the ester to the amine by the B(Al)2 (S(N)2) mechanism was observed leading to the corresponding N-methylamines under specific conditions. The reaction was accompanied by the formation of amides via B(AC)2 mechanism. The unexpected methyl transfer is highly dependent on the structure of the starting amine and is supported by the absence of solvent and high temperature. (C) 2016 Elsevier B.V. All rights reserved.