Nickel-Catalyzed Dearomative Arylboration of Indoles: Regioselective Synthesis of C2- and C3-Borylated Indolines.

Autor:	Trammel GL; Department of Chemistry, Indiana University, 800 E. Kirkwood Ave, Bloomington, Indiana 47405, United States., Kuniyil R; Department of Chemistry, University of Pittsburgh, 219 Parkman Ave, Pittsburgh, Pennsylvania 15260, United States., Crook PF; Department of Chemistry, Indiana University, 800 E. Kirkwood Ave, Bloomington, Indiana 47405, United States., Liu P; Department of Chemistry, University of Pittsburgh, 219 Parkman Ave, Pittsburgh, Pennsylvania 15260, United States., Brown MK; Department of Chemistry, Indiana University, 800 E. Kirkwood Ave, Bloomington, Indiana 47405, United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2021 Oct 13; Vol. 143 (40), pp. 16502-16511. Date of Electronic Publication: 2021 Sep 28.
DOI:	10.1021/jacs.1c05902
Abstrakt:	Indole dearomatization is an important strategy to access indolines: a motif present in a variety of natural products and biologically active molecules. Herein, a method for transition-metal catalyzed regioselective dearomative arylboration of indoles to generate diverse indolines is presented. The method accomplishes intermolecular dearomatization of simple indoles through a migratory insertion pathway on substrates that lack activating or directing groups on the C2- or C3-positions. Synthetically useful C2- and C3-borylated indolines can be accessed through a simple change in N -protecting group in high regio- and diastereoselectivities (up to >40:1 rr and >40:1 dr) from readily available starting materials. Additionally, the origin of regioselectivity was explored experimentally and computationally to uncover the remarkable interplay between carbonyl orientation of the N -protecting group on indole, electronics of the C2-C3 π-bond, and sterics. The method enabled the first enantioselective synthesis of (-)-azamedicarpin.
Databáze:	MEDLINE
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