Document Type
Article
Language
eng
Publication Date
4-18-2018
Publisher
American Chemical Society
Source Publication
Journal of Organic Chemistry
Source ISSN
0022-3263
Abstract
The catalytic system generated in situ from the tetranuclear Ru–H complex with a catechol ligand (1/L1) was found to be effective for the direct deaminative coupling of two primary amines to form secondary amines. The catalyst 1/L1 was highly chemoselective for promoting the coupling of two different primary amines to afford unsymmetric secondary amines. The analogous coupling of aniline with primary amines formed aryl-substituted secondary amines. The treatment of aniline-d7 with 4-methoxybenzylamine led to the coupling product with significant deuterium incorporation on CH2 (18% D). The most pronounced carbon isotope effect was observed on the α-carbon of the product isolated from the coupling reaction of 4-methoxybenzylamine (C(1) = 1.015(2)). A Hammett plot was constructed from measuring the rates of the coupling reaction of 4-methoxyaniline with a series of para-substituted benzylamines 4-X-C6H4CH2NH2 (X = OMe, Me, H, F, CF3) (ρ = −0.79 ± 0.1). A plausible mechanistic scheme has been proposed for the coupling reaction on the basis of these results. The catalytic coupling method provides an operationally simple and chemoselective synthesis of secondary amine products without using any reactive reagents or forming wasteful byproducts.
Recommended Citation
Arachchige, Pandula T. Kirinde; Lee, Hanbin; and Yi, Chae S., "Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines" (2018). Chemistry Faculty Research and Publications. 986.
https://epublications.marquette.edu/chem_fac/986
Comments
Accepted version. Journal of Organic Chemistry, Vol. 83, No. 9 (April 18, 2018): 4932-4947. DOI. © 2018 American Chemical Society. Used with permission.