Palladium(II)-Catalyzed Directed anti-Hydrochlorination of Unactivated Alkynes with HCl

Derosa, Joseph; Cantu, Annabelle L.; Boulous, Mark N.; O�Duill, Miriam L.; Turnbull, Joshua L.; Liu, Zhen; De La Torre, Daizy M.; Engle, Keary M.

Abstract

A regioselective anti-hydrochlorination of unactivated alkynes is reported. The reaction utilizes in situ generated HCl as the source of both the Cl - and H + and is catalyzed by palladium(II) acetate, with loadings as low as 25 ppm. Removable picolinamide and 8-aminoquinoline bidentate directing groups are used to control the regioselectivity of the chloropalladation step and stabilize the resulting alkenylpalladium(II) intermediate for subsequent protodepalladation. This method provides access to a broad array of substituted alkenyl chlorides in excellent yields and with high regioselectivity. The products from this transformation were successfully derivatized via Stille coupling to a variety of trisubstituted alkene products. Reaction progress kinetic analysis was performed, shedding light on a possible mechanism for this catalytic process.

Citation

Derosa, J., Cantu, A. L., Boulous, M. N., O’Duill, M. L., Turnbull, J. L., Liu, Z., De La Torre, D. M., & Engle, K. M. (2017). Palladium(II)-Catalyzed Directed anti-Hydrochlorination of Unactivated Alkynes with HCl. Journal of the American Chemical Society, 139(14), 5183-5193. https://doi.org/10.1021/jacs.7b00892

• Journal Article Type: Article
• Acceptance Date: Mar 7, 2017
• Online Publication Date: Mar 31, 2017
• Publication Date: Apr 12, 2017
• Deposit Date: Jun 26, 2020
• Publicly Available Date: Oct 28, 2020
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 139
• Issue: 14
• Pages: 5183-5193
• DOI: https://doi.org/10.1021/jacs.7b00892
• Keywords: Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis
• Public URL: https://nottingham-repository.worktribe.com/output/4711175
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.7b00892
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.7b00892.