摘要：Cross-Coupling Reactions withNickel, Visible Light, and tert-Butylamine as a Bifunctional Additive

转自：康龙化成

Cross-Coupling Reactions withNickel, Visible Light, and tert-Butylamine as a Bifunctional Additive

Jonas Düker, Maximilian Philipp, Thomas Lentner,Jamie A. Cadge, Joaõ E. A. Lavarda,Ruth M. Gschwind,Matthew S. Sigman, Indrajit Ghosh,* and Burkhard König*

[a] Fakultätfür Chemie und Pharmazie, Universität Regensburg, Regensburg 93040, Germany;

[b]Nanotechnology Centre, Centre for Energy and Environmental Technologies, VSB -Technical University of Ostrava, Ostrava-Poruba 708 00, Czech Republic;

[c] Departmentof Chemistry, University of Utah, 315 1400 E, Salt Lake City 84112, Utah,United States

—ACSCatal., 2025, doi:10.1021/acscatal.4c07185

Recommended by Depei Meng_MC4

KEYWORDS: photochemistry (反应类型), Nicatalysis (反应类型),C(sp2)-O, C(sp2)-N (成键类型),Aryl bromides,phenols,alcohols, anilines, sulfonamides, sulfoximines,imines (原料),NiBr2· glyme, 4CzIPN (催化剂), tert-Butylamine (试剂)

ABSTRACT: Wepresent here a general approach to nickel-catalyzed photoredox reactions employing tert-butylamine as a cost-effective bifunctional additive,acting as the base and ligand.This method proves effective for C–O and C–N bond-forming reactions with adiverse array of nucleophiles, including phenols, aliphatic alcohols, anilines,sulfonamides, sulfoximines, andimines. Notably, the protocol demonstrates significant applicability inbiomolecule derivatization and facilitates sequential one-pot functionalizations.

(A)Traditional thermal cross-coupling conditions and base-associated challenges.(B) Nickel-catalyzed etherification using amidinebase. (C) Nickel-catalyzed aniline cross-coupling using alkyl amine base. (D)Electrochemical nickel-catalyzed etherification of aliphatic alcohols. (E)Nickel photoredoxdual-catalyzed aryl amine cross-coupling using alkyl amine base. (F)tert-Butylamine as ligand and base for nickel photoredoxcross-coupling of different nucleophile classes

Syntheticexamples of C−O and C−N cross-coupling reactions

Syntheticapplications including the synthesis of complex molecules, sequential one-pot difunctionalization,and upscaling

Summary and Comments

Inconclusion, Jonas Dük et al. reporta generalcross-coupling protocol employing tert-butylamine as adual-function additive, marking a significant advancement in nickel-catalyzed photoredox chemistry.This method simplifies reaction conditions with good efficiency, demonstratingbroad applicability across various nucleophiles and electrophiles, includingbiomolecules. tert-Butylamine effectively serves as both a ligand and a base, addressing common challengesassociated with traditional bases and ligands, such as solubility issues andthe need for specific optimization. Additionally, simple and interpretablestructure−activity relationships provide a foundation for more sophisticateddata science models and enable qualitative estimation of reaction outcomes. Thecompatibility of various nucleophiles allows sequential one-pot difunctionalizations,showcasing its practicality for constructing molecular complexity and rapidcompound library generation. The homogeneous and precipitate-free nature of thesystem with cost-effective reagents facilitates convenient scaling to gramquantities and promises applicability in larger-scale processes using flowtechnology.

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