Rhodium-Catalyzed Meta-C-H Arylation of Arenes with Varied Linker Lengths: Bridging Catalytic Selectivity with Structural Diversity.

Autor: Mandal A; Department of Chemistry, Indian Institute of Technology Bombay Powai, Mumbai, 400076, India., Prasad Biswas J; Department of Chemistry, G. L. Choudhury College, Barpeta Road, Assam, 781315., Maiti D; Department of Chemistry, Indian Institute of Technology Bombay Powai, Mumbai, 400076, India.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Nov 19, pp. e202419954. Date of Electronic Publication: 2024 Nov 19.
DOI: 10.1002/anie.202419954
Abstrakt: The directing group (DG)-assisted approach has so far been the major route to achieve selective C-H activation at both proximal and distal positions. While rhodium catalysts are highly effective in DG-assisted ortho-C-H arylation, meta-C-H arylation with rhodium has not yet been reported. In this study, we present the first example of Rh-catalyzed meta-C-H arylation of arenes. We found that the 2-cyanophenyl-based directing group, in conjunction with arylboronic acids, selectively promotes meta-arylation with complete mono-selectivity. Despite significant advancements in meta-C-H activation for substrates with shorter linkers, such as hydrocinnamic acids, benzyl alcohols/amines, etc., meta-C-H activation of substrates with longer alkyl chains remains challenging with limited literature examples. We demonstrated that arenes with varying chain lengths, including conformationally flexible and less rigid ones such as 4-phenylbutanoic acid, 5-phenylvaleric acid, 6-phenylcaproic acid, 3-phenylpropanol, and 4-phenylbutanol underwent meta-arylation with high levels of regiocontrol. From a synthetic perspective, this approach could be valuable as it allows to produce biaryl derivatives of flexible arenes with native functional groups at the meta-position. The synthetic utility of this strategy is demonstrated through the total synthesis of CNBCA, a bioactive compound possessing promising potency against the SHP2 enzyme activity in vitro.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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