Document Type

Article

Language

eng

Publication Date

9-13-2018

Publisher

Elsevier

Source Publication

Tetrahedron

Source ISSN

0040-4020

Abstract

Bifunctional catalysts containing discrete metal pi-acid and amine sites were designed and investigated for the direct intermolecular addition of aldehydes and ketones to unactivated alkynes. Copper(I)-based catalysts were prioritized based on intramolecular (Conia-ene type) reactions, and complexes were designed with tridentate ligands and potentially hemilabile heterocyclic spacers. The structures of the designed catalysts were computed using density functional theory (DFT), and the relative energies of putative catalytic intermediates were estimated and used to prioritize catalyst designs. Novel bifunctional precatalysts containing a thiazole spacer were synthesized via a 9-step sequence and combined with transition metals before screening for the direct addition of aldehydes and ketones to several internal and terminal alkynes. Despite the lack of desired intermolecular reactions, DFT calculations of putative catalyst intermediates appears to be a promising strategy for the design and prioritization of bifunctional catalysts for CC bond formation.

Comments

Accepted version. Tetrahedron, Vol. 74, No. 37 (September 13, 2018): 4823-4836. DOI. © 2018) Elsevier B.V. Used with permission.

Available for download on Sunday, September 13, 2020

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