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We report the synthesis of germanyl triazoles formed via a copper-catalysed azide-alkyne cycloaddition (CuAAC) of germanyl alkynes. The reaction is often high yielding, functional group tolerant, and compatible with complex molecules. The installation of the Ge moiety enables further diversification of the triazole products, including chemoselective transition metal-catalysed cross-coupling reactions using bifunctional boryl/germyl species.

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Methyl groups rank among the most abundant carbon fragments found in natural products and small-molecule pharmaceuticals. The late-stage and environmentally friendly installation of these groups onto biologically active molecules has attracted widespread attention in both industry and academia. In 2008, we published the first use of a methyl radical derived from a peroxide toward a directed transition-metal catalysed C-H methylation.

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Ligand-enabled Ni-catalysed dicarbofunctionalisation of alkenes with diverse native functional groups.

Nat Commun

November 2024

State Key Laboratory of Organometallic Chemistry and Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (CAS), Shanghai, PR China.

The transition metal-catalysed dicarbofunctionalisation of unactivated alkenes normally requires exogenous strong coordinated directing groups, thus reducing the overall reaction efficiency. Here, we report a ligand-enabled Ni(II)-catalysed dicarbofunctionalisation of unactivated alkenes with aryl/alkenyl boronic acids and alkyl halides as the coupling partners with a diverse range of native functional groups as the directing group. This dicarbofunctionalisation protocol provides an efficient and direct route towards vicinal 1,2-disubstituted alkanes using primary, secondary, tertiary amides, sulfonamides, as well as secondary and tertiary amines under redox-neutral conditions that are challenging to access through conventional methods.

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Coupling of unactivated alkyl electrophiles using frustrated ion pairs.

Nature

December 2024

Laboratorium für Organische Chemie, ETH Zürich, Zürich, Switzerland.

Cross-electrophile coupling reactions have evolved into a major strategy for rapidly assembling important organic molecules. Two readily accessible electrophiles are coupled to form new C-C bonds, providing a key advantage over traditional cross-coupling strategies that require the preformation of reactive organometallic species. Yet, the formation of C(sp)-C(sp) bonds that form the core of nearly all organic compounds remains highly challenging with current approaches, calling for the design of innovative new strategies.

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Recent advances in the applications of -difluoromethylene alkynes.

Org Biomol Chem

November 2024

School of Chemistry and Chemical Engineering, Yangzhou University, 180 Siwangting Road, Yangzhou, Jiangsu, 225002, P.R. China.

Article Synopsis
  • -Difluoromethylene alkynes are a unique subclass of alkynes with interesting properties caused by their difluoro substitution, which affects how they react in chemical processes.
  • -Recent advancements in research focus on transition metal-catalyzed reactions involving these alkynes, showcasing various reaction pathways and mechanisms.
  • The review aims to inspire synthetic chemists by presenting elegant examples of difluoromethylene alkynes and encouraging them to explore novel chemical transformations.
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