Multifaceted Substrate-Ligand Interactions Promote the Copper-Catalyzed Hydroboration of Benzylidenecyclobutanes and Related Compounds.

Autor:	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., Xu KL; Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, California 92037, United States., Gallego GM; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Burtea A; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Nair SK; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Patman RL; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Zhou R; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., Sutton SC; Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States., McAlpine IJ; 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] 2020 Nov 06; Vol. 10 (21), pp. 13075-13083. Date of Electronic Publication: 2020 Oct 27.
DOI:	10.1021/acscatal.0c03622
Abstrakt:	A unified synthetic strategy to access tertiary four-membered carbo/heterocyclic boronic esters is reported. Use of a Cu(I) catalyst in combination with a modified dppbz ligand enables regioselective hydroboration of various trisubstituted benzylidenecyclobutanes and carbo/heterocyclic analogs. The reaction conditions are mild, and the method tolerates a wide range of medicinally relevant heteroarenes. The protocol can be conveniently conducted on gram-scale, and the tertiary boronic ester products undergo facile diversification into valuable targets. Reaction kinetics and computational studies indicate that the migratory insertion step is turnover-limiting and accelerated by electron-withdrawing groups on the dppbz ligand. Energy decomposition analysis (EDA) calculations reveal that electron-deficient P -aryl groups on the dppbz ligand enhance the T-shaped π/π interactions with the substrate and stabilize the migratory insertion transition state. Competing Interests: The authors declare no competing financial interest.
Databáze:	MEDLINE
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