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Direct and selective synthesis of primary amines from easily available precursors is attractive yet challenging. Herein, we report the rapid synthesis of primary amines from alkenes via metal-free regioselective hydroamination at room temperature. Ammonium carbonate was used as ammonia surrogate for the first time, allowing for efficient conversion of terminal and internal alkenes into linear, α-branched, and α-tertiary primary amines under mild conditions. This method provides a straightforward and powerful approach to a wide spectrum of advanced, highly functionalized primary amines which are of particular interest in pharmaceutical chemistry and other areas.

Direct alkylation of the C-H bond arenes in a selective manner is a long-standing challenge. Herein, a metal-free photocatalytic regioselective C-H alkylation method for electron-rich arenes with both activated and unactivated alkenes was developed. The reaction tolerates a wide range of aromatic rings with diverse substitution patterns, as well as terminal and internal alkenes, providing a general and straightforward metal-free method for C-C bond formation from inert C-H bonds. Moreover, alkynes are also compatible to give the C-H vinylation of electron-rich arenes.

Direct functionalizations of two distinct inert C-H bonds represent the most ideal ways to construct C-C bonds. Herein, we report an intermolecular vinylation of aldehydes using alkenes as the vinylating reagents through sequential two-fold C-H functionalizations. The merging of visible light and NHC-catalysis allows for the direct coupling of alkenes with aldehydes through an unprecedented relay dual catalysis enabled cross-dehydrogenative coupling mechanism. The use of diphenoquinone is essential for the success of this reaction, which plays an intriguing two-fold role in the reaction, as both an electron acceptor as well as a radical reservoir for the radical coupling enabling C-C forming-process.

Chiral dialkyl amines and alcohols are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective reductive hydroalkylation of enamides and enolates with alkyl halides to afford enantioenriched α-branched aliphatic amines and alcohols in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral dialkyl amine and alcohol derivatives from simple starting materials with great functional group tolerance.

Chiral dialkyl amines and alcohols are ubiquitous in pharmaceuticals, pesticides, natural products and fine chemicals, yet difficult to access due to the challenge to differentiate between the spatially and electronically similar alkyl groups. Herein, we report a nickel-catalyzed enantioselective reductive hydroalkylation of acyl enamines and enol esters with alkyl halides to afford enantioenriched α-branched aliphatic amines and alcohols in good yields with excellent levels of enantioselectivity. The operationally simple protocol provides a straightforward access to chiral dialkyl amine and alcohol derivatives from simple starting materials with great functional group tolerance.