Carbon migration of alkenyl alcohols has been recognized as an increasingly viable methodology in organic synthesis. Herein, we disclose a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp3)–C(sp3) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields. The migration proceeds via a one-pot, two-step process involving a free-state alkyl metal species.

Transfer hydrogenation between alcohols and carbonyl compounds via C-H bond cleavage is well known, whereas transfer hydrocarbylation remains a challenge due to the unactivated C-C bond cleavage. Herein, we disclose...

A non-noble Cu-catalyzed transfer aza-benzyl Michael addition via the C–C bond cleavage of aza-benzyl alcohols has been disclosed. The unstrained C(sp3)–C(sp3) bond of an alcohol was selectively cleaved. This aza-benzyl transfer strategy provides a selective and environmentally benign approach for the C-alkylation of α,β-unsaturated carbonyl compounds that employs readily available alcohols as carbon nucleophiles and is characterized by a wide range of substrates and good to excellent yields.