Catalyst Pendent-Base Effects on Cyclization of Alkynyl Amines

Authors

James M. Stubbs, The University of Western Ontario
Devon E. Chapple, The University of Western Ontario
Paul D. Boyle, The University of Western Ontario
Johanna M. Blacquiere, The University of Western OntarioFollow

Document Type

Article

Publication Date

9-7-2018

Journal

ChemCatChem

Volume

10

Issue

17

First Page

3694

Last Page

3702

URL with Digital Object Identifier

10.1002/cctc.201800713

Abstract

A family of [CpRu(PP)(MeCN)]PF6 complexes (2 a–e and 4) were prepared in which the bis-phosphine ligand contains a pendent tertiary amine in the second-coordination sphere. 2 a–e contain PPh2NR′2 ligands with two amine groups as the pendent base. Complex 4 has the PPh2NPh1 ligand with only one pendent amine. The catalytic performance of 2 a–e and 4 were assessed in the cyclization of 2-ethynyl aniline and 2-ethynylbenzyl alcohol. It was revealed that the positioning of the pendent amine near the metal active site is essential for high catalyst performance. A comparison of PPh2NR′2 catalysts (2 a–e) showed minimal difference in performance as a function of pendent amine basicity. Rather, only a threshold basicity – in which the pendent amine was more basic than the substrate – was required for high performance.