Rh-Catalyzed [8+1] Cycloaddition of Vinyl Biscyclopropanes with CO for the Synthesis of Nine-Membered Carbocycles

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4441 - 4449

Опубликована: Фев. 28, 2025

Язык: Английский

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Vinylcyclopropanes as Three-Carbon Synthons in Rhodium-Catalyzed Cycloadditions: Reaction Development, Mechanistic Studies, New Inspirations, and Synthetic Applications

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Март 17, 2025

ConspectusCyclic structures are common in natural products and pharmaceuticals, but pose major synthetic challenges. Transition metal–catalyzed cycloadditions provide a direct efficient route to complex ring systems single step. The demand for new transition remains high, as these methods enable access diverse with unique substituents stereochemistries that often unattainable through existing cycloaddition techniques. Vinylcyclopropanes (VCPs) widely recognized versatile five-carbon (C5) synthons various metal-catalyzed cycloadditions, including [5 + 1], 2], 2 1] reactions. In reactions, VCP uses its vinyl group facilitate C–C bond cleavage the strained cyclopropane, aided by metals. contrast, isolated cyclopropanes typically lack this reactivity. Building on advantages, we discovered altering connectivity between VCPs other synthons, such alkenes, alkynes, allenes, or dienes, can act novel three-carbon (C3) enabling previously unknown cycloadditions. This account outlines discoveries.By connecting two-carbon (C2) at positions 1, 2, α, created substrates, 2-trans-ene/allene-VCPs, 1-ene/yne/allene-VCPs, α-ene-VCPs. These substrates undergo [3 2] construct fused bicyclic structures. Notably, 1-ene/yne/allene-VCPs construction of 5/5 rings bridgehead quaternary centers, representing remarkable advancement. reaction has also been extended asymmetric variant, marking first kind. Furthermore, 1-ene/yne-VCPs have adapted allowing synthesis 5/6 6/6 bridged centers. utility method is demonstrated application several products. success further inspired development [4 using yne-vinylcyclobutanones (yne-VCBOs). While VCBO traditionally used six-carbon (C6) synthon, it functions four-carbon (C4) synthon when alkynes connected 1-position VCBOs. cocatalyzed Rh Zn yields which same motif formed via 1-yne-VCPs CO.The seven-membered challenging endeavor. By diene VCPs, developed Rh-catalyzed 3] cycloaddition, yielding 5/7 Additionally, introducing CO into enabled 3]/[4 generating 5/7/5 triangular scaffolds. Both reactions feature an unprecedented endo-oxidative cyclometalation mode, could be utilized future design. Further developments may include expanding scopes, applying product medicinal chemistry, realizing variants, understanding mechanisms, inventing

Язык: Английский

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Progress in [4＋1] Cycloadditions of Conjugated Dienes

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(1), С. 1 - 1

Опубликована: Янв. 1, 2025

Язык: Английский

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Rhodium-Catalyzed [5 + 1 + 2] Cycloaddition of Yne-3-Acyloxy-1,4-Enynes (YACEs) and Carbon Monoxide: Reaction Development and Mechanism

Опубликована: Апрель 4, 2024

Developing new reaction to synthesize challenging eight-membered carbocycles is a research frontier of organic synthesis. Reported here the development first Rh-catalyzed [5 + 1 2] cycloaddition yne-3-acyloxy-1,4-enyne (Yne-ACEs, short as YACEs) and CO, in which sequentially 5-carbon (generated from 3-acyloxy-1,4-enynes), 1-carbon (CO) 2-carbon (alkynes) are embedded into final 5/8 scaffold containing cyclooctatrienone structure. This has broad scope can be carried out under mild conditions. Keys success present reaction, discovered supported by experiments ab initio calculations, include: using terminal alkyne 3-acyloxy-1,4-enyne moiety substrates so that 1,2-acyloxy migration (instead 1,3-acyloxy migration, step required for competing [4 2 1] reaction) realized; applying electron-rich aryl group (here p-dimethylamino aryl) acyloxy make pathway disfavored. Quantum chemical calculations have also been used answer why this but not (where insertion ahead CO insertion), factors disfavoring competitive 2], reactions.

Язык: Английский

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Rhodium-Catalyzed [5 + 1 + 2] Cycloaddition of Yne-3-acyloxy-1,4-enynes (YACEs) and Carbon Monoxide: Reaction Development and Mechanism

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 14595 - 14605

Опубликована: Сен. 17, 2024

Язык: Английский

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