Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер 13(4)

Опубликована: Янв. 3, 2024

Abstract Enynones and enynals represent donor‐type carbene precursors that efficiently form furyl metal carbenes via a catalytic intramolecular 5‐exo‐dig cyclization rearrangement cascade, in 100 % atom‐economical manner, using various metals. These have been successfully utilized numerous reactions, including X−H insertion, cyclopropanations, metathesis, cross‐coupling, demonstrating broad reaction scope efficiency constructing highly functionalized furans. Recent years witnessed significant advancements transformations involving carbenes, especially asymmetric insertion domino reactions zwitterionic intermediates, strategies, their application synthesizing functional materials drug candidates. In this review, we summarize recent progress generated from enynones enynals, focusing on the synthesis of

Язык: Английский

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Conformational Locking Induced Enantioselective Diarylcarbene Insertion into B−H and O−H Bonds Using a Cationic Rh(I)/Diene Catalyst

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 18, 2024

Abstract Transition‐metal‐catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)‐complexes. Herein, we describe our development a novel cationic Rh(I)/chiral diene catalytic system capable efficient B−H and O−H insertions with diaryl diazomethanes, allowing access broad range gem ‐diarylmethine boranes ethers good yields high enantioselectivities. Notably, previously unattainable asymmetric diarylcarbene insertion into bond was achieved for first time. A remarkable feature this newly designed Rh(I)/diene catalyst bearing ortho ‐amidophenyl substitutents is that it can distinguish through stereochemically selective control π–π stacking interactions. DFT calculations indicate rotation‐restricted conformation complex played an important role highly transformations. This work provides interesting unprecedented stereocontrol mode metal

Язык: Английский

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A combined experimental and computational study reveals a crossover between conventional cross-coupling and carbene insertion pathways in a Pd catalyzed C(sp²)–H insertion

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Computational (DFT and DLPNO-CCSD(T)) calculations along with experimental tools (deuterium labelling, kinetic studies using VTNA, ESI-HRMS UV) are used to probe the mechanism of a Pd(ii)-catalyzed enantioselective carbene insertion into C(sp2)-H indole. Using deuterium labelling studies, we demonstrate intermediacy metal-hydride species, which contrasts mechanistic routes for other transition metals (Rh, Fe, Au, Cu, etc.). Our VTNA study reveals order be one in both diazo indole, microkinetic modelling aligns well computationally predicted mechanism. The is further supported by detection most stable intermediate catalytic cycle ESI-HRMS. An investigation origin stereoselectivity DLPNO-CCSD(T) presents new paradigm, wherein stereocontrol arises during formation Pd itself as opposed proton transfer steps found all metal catalysts.

Язык: Английский

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Conformational Locking Induced Enantioselective Diarylcarbene Insertion into B−H and O−H Bonds Using a Cationic Rh(I)/Diene Catalyst

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Июль 18, 2024

Abstract Transition‐metal‐catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)‐complexes. Herein, we describe our development a novel cationic Rh(I)/chiral diene catalytic system capable efficient B−H and O−H insertions with diaryl diazomethanes, allowing access broad range gem ‐diarylmethine boranes ethers good yields high enantioselectivities. Notably, previously unattainable asymmetric diarylcarbene insertion into bond was achieved for first time. A remarkable feature this newly designed Rh(I)/diene catalyst bearing ortho ‐amidophenyl substitutents is that it can distinguish through stereochemically selective control π–π stacking interactions. DFT calculations indicate rotation‐restricted conformation complex played an important role highly transformations. This work provides interesting unprecedented stereocontrol mode metal

Язык: Английский

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An Improved Synthesis of Chiral 2,2′-Bipyridine Ligand C3-ACBP Without Column Chromatography

Synthesis, Год журнала: 2023, Номер 55(16), С. 2483 - 2486

Опубликована: Март 27, 2023

Abstract A method for purifying compounds bearing pyridine structure from Mitsunobu reaction mixtures using zinc chloride and releasing bipyridines Ullmann coupling by sulfide anion competitively coordinating the copper ion were developed facile synthesis of chiral 2,2′-bipyridine ligand (Ra ,S,S)-C3-ACBP. With these improvements, an improved at a 7 gram scale has been fulfilled in 48% overall yield without column chromatography within 3–4 days.

Язык: Английский

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Heterocycles from Donor and Donor/Donor Carbenes

Topics in heterocyclic chemistry, Год журнала: 2023, Номер unknown, С. 269 - 312

Опубликована: Янв. 1, 2023

Язык: Английский

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