Metal-catalysed C–C bond formation at cyclopropanes

Nickel-catalyzed γ-alkylation of cyclopropyl ketones with unactivated primary alkyl chlorides: balancing reactivity and selectivity via halide exchange

“…Cyclopropyl ketones serve as valuable building blocks, readily attainable from diverse initial substrates, 5 facilitating the synthesis of γ-functionalized ketone molecules via ring-opening reactions. 6 …”

Alkyl Cyclopropyl Ketones in Catalytic Formal [3 + 2] Cycloadditions: The Role of SmI2 Catalyst Stabilization

“…The ability to construct complex molecular frameworks akin to Nature’s building blocks is a fundamental goal of synthetic organic chemistry. Modular routes to such frameworksespecially those involving catalytic reactionsare particularly sought after, as they enable the efficient construction of highly relevant compound libraries that can be used to unlock the correlation between compound structure and biological activity in, for example, the pharmaceutical and agrochemical industries (Figure A). , Recent years have seen intense interest in the exploitation of cyclopropyl ketones in formal [3 + 2] cycloaddition reactions with alkene and alkyne partners under radical and photochemical/photocatalytic conditions. − Crucially, advancements in this area have been firmly limited to employing aryl cyclopropyl ketone starting materials (Figure B), leading to products largely incongruent with Nature’s sp 3 -rich building blocks. The reason for this significant limitation and the major challenge associated with the reduction of unactivated aliphatic carbonyl compounds is their low standard redox potential (e.g., cyclohexanone E 1/2 = −2.73 V vs SCE) .…”

Silver-Catalyzed Radical Umpolung Cross-Coupling of Silyl Enol Ethers with Activated Methylene Compounds: Access to Diverse Tricarbonyl Derivatives

“…Catalytic radical carbon–carbon (C–C) cross-coupling reactions constitute privileged platforms in chemical synthesis, especially for the synthesis of natural products, pharmaceuticals, and materials. , Although significant progress has been achieved over the past two decades, there is still strong interest in developing novel radical C–C coupling reactions using platform chemicals.…”