Oct 2026· Angewandte Chemie· pp.
e6256116
· 0 citations· 42 references
Medicine
Abstract
The use of ester-derived electrophiles in transition-metal-free electroreductive C(sp3)─C(sp3) bond formation remains largely unexplored. Herein, we report a sacrificial-anode-enabled electroreductive cross-coupling of simple unsaturated carboxylates with unactivated alkyl halides. Aryl, alkenyl, and alkynyl carboxylates are readily incorporated, affording methylene-bridged alkylarenes together with allylic and propargylic C(sp3)-rich frameworks under mild conditions. Mechanistic studies support independent single-electron reduction of both electrophilic partners, followed by radical-radical coupling, alkoxide elimination, and cathodic deoxygenation via a Clemmensen-like reduction pathway. This work establishes unsaturated carboxylates as a new class of alkylating reagents for electroreductive C(sp3)─C(sp3) bond formation.
Given the thermodynamic stability of the C(sp2)–O bond, the development of simple and efficient strategies for its functionalization holds significant practical value. In this study, we report an electroreductive, one-pot nickel-catalyzed cross-electrophile coupling (XEC) of aryl/alkenyl triflates with diverse (1°, 2...
Yi-Kun Ji, Xue-Ting Zhang, Zhou-Hang Wang et al.· ACS Catalysis· 0 citations
Radical-mediated transition-metal-catalyzed C─H carbonylation represents a direct and powerful approach for the synthesis of carbonyl compounds; however, the stoichiometric oxidants typically required for hydrogen atom abstraction hamper the extensive application of these protocols and raise environmental concerns. In...
Cheng-Cheng Fan, Jia-Ning Wu, Peng Wang et al.· Angewandte Chemie· 0 citations
Direct activation of native C(sp2)–NH2 bonds in alkenyl amines remains a largely unmet challenge in cross-coupling chemistry owing to their high bond dissociation energies, poor leaving-group ability, and competing tautomerization pathways. Herein, we report a nickel-catalyzed tandem deaminative coupling/alkene isome...
In the present work, we have developed a dual triplet ketone/nickel-catalyzed strategy for C(sp3)-C(sp2) and C(sp3)-C(sp3) cross-coupling between aryl/alkyl bromides and alkyl boronic acids/boronates via an aminyl radical transfer (ART) strategy. The protocol features several attractive advantages, including mild react...
Amit Behera, Akash Bisoyi, G. G. et al.· Organic Letters· 0 citations
Carbon-carbon bond-forming reactions are central to medicinal chemistry efforts. Methods that utilise abundant and structurally diverse building blocks can accelerate chemical space exploration in drug discovery. Herein, we report an electrochemical deaminative-decarboxylative cross-coupling reaction to form C(sp3)-C(s...
Bing-Qing Tang, Jennifer Morvan, Filippo Begal et al.· Organic and biomolecular che...· 0 citations
A visible-light-driven nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl iodides has been developed using 9-fluorenone (FLN) as an inexpensive organic photosensitizer. The readily available FLN/diisopropylethylamine system enables C(sp2)-C(sp3) bond formation in moderate to high yields under mild...
Yu-Miao Zhao, Shi-Lei Yang, Li-Ran Wang et al.· Organic and biomolecular che...· 0 citations
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