Regiospecificity in Ligand-Free Pd-Catalyzed C–H Arylation of Indoles: LiHMDS as Base and Transient Directing Group

Regiospecificity in Ligand-Free Pd-Catalyzed C–H Arylation of Indoles: LiHMDS as Base and Transient Directing Group

A highly efficient catalyst–base pair for the C–H arylation of free (NH)-indoles in the C-3 position is reported. Ligand-free palladium acetate coupled with lithium hexamethyldisilazide (LiHMDS) catalyzed the regiospecific, i.e. 100% regioselective, C-3 arylation of indoles with high turnover number...

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Veröffentlicht in:ACS catalysis 2020-02, Vol.10 (4), p.2713-2719
Hauptverfasser: Mohr, Yorck, Renom-Carrasco, Marc, Demarcy, Clément, Quadrelli, Elsje Alessandra, Camp, Clément, Wisser, Florian M, Clot, Eric, Thieuleux, Chloé, Canivet, Jérôme
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container_end_page 2719
container_issue 4
container_start_page 2713
container_title ACS catalysis
container_volume 10
creator Mohr, Yorck
Renom-Carrasco, Marc
Demarcy, Clément
Quadrelli, Elsje Alessandra
Camp, Clément
Wisser, Florian M
Clot, Eric
Thieuleux, Chloé
Canivet, Jérôme
description A highly efficient catalyst–base pair for the C–H arylation of free (NH)-indoles in the C-3 position is reported. Ligand-free palladium acetate coupled with lithium hexamethyldisilazide (LiHMDS) catalyzed the regiospecific, i.e. 100% regioselective, C-3 arylation of indoles with high turnover numbers. This catalytic system has been successfully applied to a wide range of substrates, including various functional aryl halides and indolic cores. The unique role of LiHMDS as both a base and unexpected transient directing group has been revealed experimentally and elucidated computationally, in line with a Heck-type insertion–elimination mechanism.
doi_str_mv 10.1021/acscatal.9b04864
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title Regiospecificity in Ligand-Free Pd-Catalyzed C–H Arylation of Indoles: LiHMDS as Base and Transient Directing Group
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