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Nickel-Catalyzed Dearomative Arylboration of Indoles: Regioselective Synthesis of C2- And C3-Borylated Indolines
G.L. Trammel, , P.F. Crook, P. Liu, M.K. Brown
Published in American Chemical Society
2021
PMID: 34582691
Volume: 143
   
Issue: 40
Pages: 16502 - 16511
Abstract
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. ©
About the journal
JournalData powered by TypesetJournal of the American Chemical Society
PublisherData powered by TypesetAmerican Chemical Society
ISSN00027863