Diverse radical transformations of allenic C(sp)-C(sp<sup>2</sup>) and C(sp<sup>3</sup>)-C(sp<sup>2</sup>) bonds enabled by silyl substitution.
basic_science · Level V
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- Record sourced from PubMed, PMID 42362578.
- Also identified by DOI 10.1038/s41467-026-74846-8.
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Abstract
While the oxidative cleavage of olefins is well established, the radical-mediated, chemo- and regioselective cleavages of allene C(sp)-C(sp<sup>2</sup>) and C(sp<sup>3</sup>)-C(sp<sup>2</sup>) bonds remain unresolved challenges in synthetic chemistry. These challenges primarily stem from the high reactivity of the unique twisted orthogonal π-systems and the regioselectivity issues associated with adjacent C = C double bonds. Herein, we present base metal-catalyzed cleavage of allenic C(sp)-C(sp<sup>2</sup>) double bonds and C(sp<sup>3</sup>)-C(sp<sup>2</sup>) single bonds utilizing air as an oxidant. These transformations, initiated by hydrogen atom abstraction (HAA) from the allenic C(sp<sup>2</sup>)-H bonds, lead to the formation of a diverse range of remotely functionalized ketones, alkylated heteroaryls, alkylated nitriles, and deuterated products, all with remarkable site selectivity. In this strategy, the α-silyl effect plays a key role in activating allenic C(sp<sup>2</sup>)-H bond thus initiating the HAA from allenes and achieving the desired regioselectivity.