Transition metal-catalysed functionalizations of inert C-H bonds to construct C-C bonds represent an ideal route in the synthesis of valuable organic molecules. Fine tuning of directing groups, catalysts and ligands has played a crucial role in selective C-H bond (sp or sp) activation. Recent developments in these areas have assured a high level of regioselectivity in C-H olefination reactions. In this review, we have summarized the recent progress in the oxidative olefination of sp and sp C-H bonds with special emphasis on distal, atroposelective, non-directed sp and directed sp C-H olefination. The scope, limitation, and mechanism of various transition metal-catalysed olefination reactions have been described briefly.
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http://dx.doi.org/10.1039/d0sc05555g | DOI Listing |
Beilstein J Org Chem
December 2024
EaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, Fife, KY16 9ST, UK.
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.
View Article and Find Full Text PDFChem Sci
January 2025
Department of Chemistry, McGill University 801 Sherbrooke Street West Montreal Quebec H3A 2K6 Canada
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.
View Article and Find Full Text PDFNat 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.
View Article and Find Full Text PDFNature
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.
View Article and Find Full Text PDFOrg Biomol Chem
November 2024
School of Chemistry and Chemical Engineering, Yangzhou University, 180 Siwangting Road, Yangzhou, Jiangsu, 225002, P.R. China.
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