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Organic Letters· 2026Q1

γ-Selective Deuteration of Unactivated C(sp3)–H Bonds of Aliphatic Amines via Pd Catalysis in D2O

Jian‐Fei Bai, Hao Hu, Ru Bo, Jianbo Tang et al.

Short summary

A new Pd-catalyzed method achieves selective deuteration at the γ-position of unactivated C(sp3)–H bonds in aliphatic amines using D2O as the deuterium source and 3-formyl-2-pyridone as a transient directing group.

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Abstract

Abstract Selective γ-deuteration of unactivated C(sp3)–H bonds in aliphatic amines is achieved using D2O as the sole deuterium source via Pd catalysis with 3-formyl-2-pyridone as a transient directing group. The reaction proceeds in aqueous medium without acidic or fluorinated co-solvents. Branched and cyclic amines are deuterated regioselectively at γ-methyl sites (up to 89% D). The utility is demonstrated by concise synthesis of deuterated scaffolds (rimantadine, ethambutol, and dobutamine) otherwise inaccessible by conventional methods, together with a one-pot γ-deuteration/γ-arylation sequence. Mechanistic studies establish that the pyridone moiety dominates the CMD step and intrinsically favors H/D exchange.

The authors' abstract, as published at the source. Organic Letters, 2026 · DOI ↗

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