Tridentate Directing Groups Stabilize 6-Membered Palladacycles in Catalytic Alkene Hydrofunctionalization

O�Duill, Miriam L.; Matsuura, Rei; Wang, Yanyan; Turnbull, Joshua L.; Gurak, John A.; Gao, De-Wei; Lu, Gang; Liu, Peng; Engle, Keary M.

Abstract

Removable tridentate directing groups inspired by pincer ligands have been designed to stabilize otherwise kinetically and thermodynamically disfavored 6-membered alkyl palladacycle intermediates. This family of directing groups enables regioselective remote hydrocarbofunctionalization of several synthetically useful alkene-containing substrate classes, including 4-pentenoic acids, allylic alcohols, homoallyl amines, and bis-homoallylamines, under Pd(II) catalysis. In conjunction with previous findings, we demonstrate regiodivergent hydrofunctionalization of 3-butenoic acid derivatives to afford either Markovnikov or anti-Markovnikov addition products depending on directing group choice. Preliminary mechanistic and computational data are presented to support the proposed catalytic cycle.

Citation

O’Duill, M. L., Matsuura, R., Wang, Y., Turnbull, J. L., Gurak, J. A., Gao, D.-W., Lu, G., Liu, P., & Engle, K. M. (2017). Tridentate Directing Groups Stabilize 6-Membered Palladacycles in Catalytic Alkene Hydrofunctionalization. Journal of the American Chemical Society, 139(44), 15576-15579. https://doi.org/10.1021/jacs.7b08383

• Journal Article Type: Article
• Acceptance Date: Oct 3, 2017
• Online Publication Date: Oct 26, 2017
• Publication Date: Nov 8, 2017
• Deposit Date: Jun 26, 2020
• Publicly Available Date: Aug 24, 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: 44
• Pages: 15576-15579
• DOI: https://doi.org/10.1021/jacs.7b08383
• Keywords: Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis
• Public URL: https://nottingham-repository.worktribe.com/output/4711194
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.7b08383
• 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.7b08383.