Ni-Catalyzed Traceless, Directed C3-Selective C-H Borylation of Indoles
- 29 July 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (30), 13136-13144
- https://doi.org/10.1021/jacs.0c05434
Abstract
A highly efficient and general protocol for traceless, directed C3-selective C-H borylation of indoles with [Ni(IMes)(2)] as the catalyst is reported. Activation and borylation of N-H bonds by [Ni(IMes)(2)] is essential to install a Bpin moiety at the N-position as a traceless directing group, which enables the C3-selective borylation of C-H bonds. The N-Bpin group which is formed is easily converted in situ back to an N-H group by the oxidative addition product of [Ni(IMes)(2)] and in situ-generated HBpin. The catalytic reactions are operationally simple, allowing borylation of a variety of substituted indoles with B(2)pin(2) in excellent yields and with high selectivity. The C-H borylation can be followed by Suzuki-Miyaura cross-coupling of the C-borylated indoles in an overall two-step, one-pot process providing an efficient method for synthesizing C3-functionalized heteroarenes.Funding Information
- Deutsche Forschungsgemeinschaft (MA 4471/4-1, RA 720/12-2)
- China Scholarship Council
- Julius-Maximilians-Universit?t W?rzburg
- Alexander von Humboldt-Stiftung
- Natural Sciences and Engineering Research Council of Canada
This publication has 107 references indexed in Scilit:
- Hydrazone as the Directing Group for Ir-Catalyzed Arene Diborylations and Sequential FunctionalizationsJournal of the American Chemical Society, 2012
- Double-Fold C–H Oxygenation of Arenes Using PyrDipSi: a General and Efficient Traceless/Modifiable Silicon-Tethered Directing GroupJournal of the American Chemical Society, 2012
- Update 1 of: Synthesis and Functionalization of Indoles Through Palladium-Catalyzed ReactionsChemical Reviews, 2011
- Palladium-Catalyzed Ligand-Directed C−H Functionalization ReactionsChemical Reviews, 2010
- Catalytic Functionalization of Indoles in a New DimensionAngewandte Chemie, 2009
- Boc Groups as Protectors and Directors for Ir-Catalyzed C−H Borylation of HeterocyclesThe Journal of Organic Chemistry, 2009
- Rhodium-Catalyzed C−C Bond Formation via Heteroatom-Directed C−H Bond ActivationChemical Reviews, 2009
- Ir-Catalyzed Functionalization of 2-Substituted Indoles at the 7-Position: Nitrogen-Directed Aromatic BorylationJournal of the American Chemical Society, 2006
- Fluorine chemistry at the millenniumJournal of Fluorine Chemistry, 2005
- Palladium-Catalyzed Cross-Coupling Reactions of Organoboron CompoundsChemical Reviews, 1995