Catalyst-controlled directing group translocation in the site selective C–H functionalization of 3-carboxamide indoles and metallocarbenes

Kuang Gu, Mary T. Hall, Zachary D. Tucker, Gregory M. Durling and Brandon L. Ashfeld ()
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Kuang Gu: University of Notre Dame
Mary T. Hall: University of Notre Dame
Zachary D. Tucker: University of Notre Dame
Gregory M. Durling: University of Notre Dame
Brandon L. Ashfeld: University of Notre Dame

Nature Communications, 2025, vol. 16, issue 1, 1-9

Abstract: Abstract Complementary methods toward the selective functionalization of indole and oxindole frameworks employing an alternative strategy in heteroaryl C–H functionalizations are presented herein. This work focuses on a catalyst-controlled, site selective C–H activation/functionalization of 3-acyl indoles, wherein an amide serves as a robust and versatile directing group capable of undergoing concomitant 1,2-acyl translocation/C–H functionalization in the presence of a RhI/AgI co-catalysts to provide the cross-coupled adducts in high yields. In contrast, the use of IrIII/AgI catalysts subverted the 1,2-acyl migration to afford the corresponding C2-functionalized products in good to excellent yields. A notable feature of the catalyst systems was the exceptional level of site selectivity observed in which the corresponding C–H functionalized indoles were obtained exclusively. Mechanistic experiments indicate a concerted 1,2-acyl migration step and indole metallation occurring through an electrophilic aromatic substitution process.

Date: 2025
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DOI: 10.1038/s41467-024-55246-2

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