Hydroamination of diphenylbutadiyne with secondary N-methyl-anilines using the dipotassium tetrakis(2,6-diisopropylanilino)calciate precatalyst

Abstract

The approved precatalyst [K₂Ca{N(H)Dipp}₄] was employed to study the hydroamination of diphenylbutadiyne with N-methyl-anilines in tetrahydrofuran at room temperature. The hydroamination occurs regioselectively within a few hours yielding (N-methyl)-(N-aryl)-1,4-diphenylbut-1-ene-3-yne-1-ylamine with phenyl (1a), 4-tolyl (1b) and 4-fluorophenyl groups (1c). In all cases a mixture of E- and Z-isomers is obtained. The second hydroamination step requires drastically extended reaction times and is successful only for the reaction of diphenylbutadiyne with N-methyl-aniline and N-methyl-4-fluoroaniline giving 1,4-diphenyl-1,4-bis(N-methyl-anilino)buta-1,3-diene [R = H (2a) and F (2c)]; a mixture of E,E-, E,Z- and Z,Z-isomers is obtained. The X-ray structures of E-1a, E-1b and E-1c show a slightly shortened N–C bond to the alkene moieties. Due to enhanced steric strain the anilino units of Z,Z-2c and Z,Z-3 turn away from the butadiene unit and consequently, the lone pair at the planar nitrogen atoms slightly interacts with the adjacent aryl groups.