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A metal‐free heterogeneous protocol is established herein for the synthesis of value‐added γ‐amino acid scaffolds via carbocarboxylation of alkenes with CO2 and alkylamines under visible light irradiation. The protocol shows broad substrate scope under mild reaction conditions and good stability of the catalyst for recycle tests. Moreover, the methodology could be feasible to the late‐stage derivatization of several natural products, enriching the chemical arsenal for practical application. [ABSTRACT FROM AUTHOR]

Light‐driven fixation of CO2 in organics has emerged as an appealing alternative for the synthesis of value‐added fine chemicals. Challenges remain in the transformation of CO2 as well as product selectivity due to its thermodynamic stability and kinetic inertness. Here we develop a boron carbonitride (BCN) with the abundant terminal B/N defects around the mesoporous walls, which essentially enhances surface active sites as well as charge transfer kinetics, boosting the overall rate of CO2 adsorption and activation. In this protocol, anti‐Markovnikov hydrocarboxylation of alkenes with CO2 to an extended carbon chain is achieved with good functional group tolerance and specific regioselectivity under visible‐light irradiation. The mechanistic studies demonstrate the formation of CO2 radical anion intermediate on defective boron carbonitride, leading to the anti‐Markovnikov carboxylation. Gram‐scale reaction, late‐stage carboxylation of natural products and synthesis of anti‐diabetic GPR40 agonists reveal the utility of this method. This study sheds new insight on the design and application of metal‐free semiconductors for the conversion of CO2 in an atom‐economic and sustainable manner. [ABSTRACT FROM AUTHOR]