Issue 14, 2016

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
30 ستمبر 2015
Accepted
18 نومبر 2015
First published
20 نومبر 2015

Dalton Trans., 2016,45, 6241-6250

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

F. M. Younis, S. Krieck, H. Görls and M. Westerhausen, Dalton Trans., 2016, 45, 6241 DOI: 10.1039/C5DT03818A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements