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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.

Visible light driven nitrene transfer and insertion reactions of organic azides are an attractive strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(iii) porphyrin catalysed sp3 C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical reactions display chemo- and regio-selectivity and are effective for the late-stage functionalization of natural and bioactive compounds with complexity. Mechanistic studies revealed that iron porphyrin plays a dual role as a photosensitizer and as a catalyst giving rise to a reactive iron–nitrene intermediate for subsequent C–N bond formation., An iron(iii) porphyrin catalysed sp3 C–H amination and alkene aziridination with broad substrate scope under mild conditions is conducted, with selectivity through the use of organic azides as the nitrogen source under blue LED light irradiation.

[FeIII(TF4DMAP)Cl] can efficiently catalyze intermolecular sp3 C–H amination using aryl azides and intramolecular sp3 C–H amination of alkyl azides in moderate-to-high product yields. At catalyst loading down to 1 mol %, the reactions display high chemo- and regioselectivity with broad substrate scope and are effective for late-stage functionalization of complex natural/bioactive molecules.

[FeIII(TF4DMAP)OTf] catalysed anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and the transformation of N-methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant with moderate to good product yields.