Cu-Catalyzed Hydroboration of Benzylidenecyclopropanes: Reaction Optimization, (Hetero)Aryl Scope, and Origins of Pathway Selectivity.

Autor:	Medina JM; Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States., Kang T; Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States., Erbay TG; Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States., Shao H; Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States., Gallego GM; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Yang S; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Tran-Dubé M; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Richardson PF; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Derosa J; Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States., Helsel RT; Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States., Patman RL; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Wang F; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Ashcroft CP; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Braganza JF; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., McAlpine I; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Liu P; Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States., Engle KM; Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Jazyk:	angličtina
Zdroj:	ACS catalysis [ACS Catal] 2019 Dec 06; Vol. 9 (12), pp. 11130-11136. Date of Electronic Publication: 2019 Oct 29.
DOI:	10.1021/acscatal.9b03557
Abstrakt:	The copper-catalyzed hydroboration of benzylidenecyclopropanes, conveniently accessed in one step from readily available benzaldehydes, is reported. Under otherwise identical reaction conditions, two distinct phosphine ligands grant access to different products by either suppressing or promoting cyclopropane opening via β-carbon elimination. Computational studies provide insight into how the rigidity and steric environment of these different bis-phosphine ligands influence the relative activation energies of β-carbon elimination versus protodecupration from the key benzylcopper intermediate. The method tolerates a wide variety of heterocycles prevalent in clinical and pre-clinical drug development, giving access to valuable synthetic intermediates. The versatility of the tertiary cyclopropylboronic ester products is demonstrated through several derivatization reactions. Competing Interests: The authors declare no competing financial interest.
Databáze:	MEDLINE
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