（来源：康龙化成）
转自：康龙化成
Photocatalytic C(sp3)–C(sp3) Cross-coupling of Carboxylic Acids and Alkyl Halides Using a Nickel Complex and Carbon Nitride
Miguel M. de Vries Ibáñez 1, Luis A. Cipriano1, Valeria Lagostina 2, Andrea Olivati 3,4, Mario Chiesa 2, Annamaria Petrozza 3, Giovanni Di Liberto 5& Gianvito Vilé 1*
1 Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, Milano, Italy. 2 Department of Chemistry, University of Torino, Torino, Italy. 3 Center for Nanoscience and Technology, IstitutoItaliano di Tecnologia, Milano, Italy. 4 Physics Department, Politecnico di Milano, Milano, Italy. 5 Department of Materials Science, University of Milano Bicocca, Milano, Italy.
—Nat.Commun., 2025, 16, 7016.
Recommended by Bingbing Chang_MC5
KEY WORDS: photo chemistry, Ni catalysis, cross-coupling (反应类型), C(sp3)–C(sp3) (成键类型), alkyl halides, carboxylic acids (反应物), carbon nitride nanosheets, nCNx (其他).
ABSTRACT: Developing robust catalytic methods for constructing C(sp3)–C(sp3) bonds is critically important for synthesizing a diverse array of drug molecules. However, this type of reaction poses significant challenges from a chemical standpoint due to issues with regioselectivity, functional group tolerance and complex catalyst design. Current metal aphotoredox approaches do not provide a viable solution because they rely on expensive, toxic, and rare iridium-based photocatalysts, severely limiting their widespread application. Prof. Gianvito Vilé et al.introduce carbon nitride nanosheets as an efficient and sustainable alternative to traditional photocatalysts. When combined with nickel, carbon nitride nanosheets facilitates the cross-coupling of alkyl halides and carboxylic acids. Our results demonstrate a broad substrate scope and highlight the recyclability of the photocatalyst. Density functional theory calculations provide molecular insights into the role of the catalytic system in facilitating photodecarboxylation and subsequent C-C bond formation. This work expands the potential of photoredox chemistry, and offers a novel method for efficient, industrially relevant light-to-chemical conversion processes.
Methods for the formation of the C(sp3)–C(sp3) bonds
Synthesisof nCNx photocatalyst
Decarboxylative C(sp3)–C(sp3) cross-coupling reaction scope (selected)
Proposed dual catalytic reaction mechanisms
Prof. Gianvito Vilé et al. have successfully developed a highly effective approach for
C(sp3)–C(sp3) cross-coupling reactions using a photocatalytic systembased on carbon nitride (nCNx)and a nickel complex.This innovative method, driven by visible light and utilizing only earth abundant elements, achieves a remarkable maximum yield of 77% for the target compound 3a. Their process is both selective and efficient, eliminating the need for preactivation of the photocatalyst, a significant advantage that simplifies the reaction setup and enhances practicality. The reaction conditions were optimized to enable broad applicability across a wide range of substrates, including cyclic and linear α-amino carboxylic acids as well as various alkyl bromides. This versatility facilitated applications such as the functionalization of pharmaceuticals like levodopa or lysine. The simplicity, efficiency, and reliance on nonprecious materials make this approach a significant advancement in developing environmentally friendly synthetic methods for pharmaceuticals and other fine chemicals.
