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Mapping the molecular mechanism of zinc catalyzed Suzuki-Miyaura coupling reaction: a computational study.

Org Biomol Chem

January 2025

Department of Chemistry, CMS College Kottayam (Autonomous), Kottayam, Kerala, 686001, India.

The Suzuki-Miyaura Coupling (SMC) reaction is a powerful method for forming carbon-carbon bonds in organic synthesis. Recent advancements in SMC reactions have introduced first-row transition metal catalysts, with zinc garnering significant interest due to its cost-effective and eco-friendly nature. Despite progress in experimental protocols, the mechanistic details of zinc-catalyzed SMC reactions are limited.

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Benzothiazolium salts as versatile primary alcohol derivatives in Ni-catalyzed cross-electrophile arylation/vinylation.

Org Biomol Chem

January 2025

Center for Supramolecular Chemistry and Catalysis and Department of Chemistry, Shanghai University, 99 Shang-Da Road, Shanghai 200444, China.

Herein, we report a Ni-catalyzed cross-electrophile coupling of aryl/vinyl halides with benzothiazolium salts derived from alcohols. Our findings demonstrate that primary alkyl benzothiazolium salts serve as effective C(sp)-O substrates, facilitating coupling with aryl and vinyl halides. This method not only enables the formal functionalization of primary alcohols but also provides experimental support for previously established sequential alcohol halogenation and Ni-catalyzed reductive coupling platforms.

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Buchwald-Hartwig (BH) aminations are crucial for synthesizing arylamine motifs in numerous bioactive molecules and fine chemicals. While homogeneous palladium complexes can be effective catalysts, their high costs and environmental impact motivate the search for alternative approaches. Heterogeneous palladium single-atom catalysts (SAC) offer promising recoverable alternatives in C-C cross-couplings.

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Nitriles are valuable compounds because they have widespread applications in organic chemistry. This report details the nickel-catalyzed reductive cyanation of aryl halides and epoxides with cyanogen bromide for the synthesis of nitriles. This robust protocol underscores the practicality of using a commercially available and cost-effective cyanation reagent.

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We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides and alkylzinc reagents. The reaction is enabled by amine coordination and can use all primary, secondary, and tertiary amines. The reaction constructs two new C(sp)-C(sp) and C(sp)-C(sp) bonds and produces δ- and ε-arylamines with C(sp)-branching at the γ- and δ-positions.

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