Metal Acetylides in Cycloaddition Reactions

Comas-Barceló, Júlia; Harrity, Joseph P. A.

doi:10.1055/s-0036-1588922

Cited by 5 publications

(2 citation statements)

References 65 publications

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“…Interestingly, a line can be drawn between the methodology limitations we observed and those that have been previously tackled in classical (3 + 2) reactions between 1,3-dipoles and terminal alkynes (Figure C). The copper-catalyzed azide–alkyne coupling (CuAAC), which makes advantageous use of metal acetylide intermediates, was an important gateway to the use of 1,3-dipolar cycloadditions in click chemistry. , By coupling the rate enhancement offered by metal acetylide catalysis with the (3 + 2) cycloaddition cascades of neutral TACs, previously underperforming reactions would be greatly enabled, and a multitude of unexplored chemical avenues could be envisaged.…”

Section: Introductionmentioning

confidence: 99%

Copper and Silver Catalysis in the (3 + 2) Cycloaddition of Neutral Three-Atom Components with Terminal Alkynes

Campeau,

Pommainville,

Gorodnichy

et al. 2023

J. Am. Chem. Soc.

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The introduction of the copper-catalyzed azide− alkyne coupling (CuAAC) to 1,3-dipolar cycloadditions was pivotal to their popularization in synthetic chemistry and to their application to multiple other domains of science. The reaction rate enhancement observed when coinage metal acetylide intermediates are involved in the cyclization process greatly expanded the structural and conditional range in which (3 + 2) cycloadditions may take place with terminal alkynes. Herein, we report that comparable rate enhancements, in nature and level, are induced by copper and silver catalysts in the intramolecular (3 + 2) cycloaddition of terminal alkynes with "neutral" three-atom components (TACs), specifically alkynyl sulfides. Through careful observations amidst reaction optimization, experimental, and DFT mechanistic studies, a pathway involving a proton-coupled cyclometallation key step is proposed. The sets of catalytic conditions that have been developed allow us to overcome several scope limitations previously presented by the thermally promoted (3 + 2) cycloaddition of "neutral" TACs, thus expanding their synthetic and applicative potential.

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Section: Introductionmentioning

confidence: 99%

Copper and Silver Catalysis in the (3 + 2) Cycloaddition of Neutral Three-Atom Components with Terminal Alkynes

Campeau,

Pommainville,

Gorodnichy

et al. 2023

J. Am. Chem. Soc.

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“…In developing catalytic methods for alkyne functionalization, the multifaceted interactions between terminal alkynes and transition metals have served as a versatile platform, on which metal π-alkyne, σ-alkynyl, and vinylidene complexes are targeted as key intermediates. However, rarely has the catalysis that interweaves the differential reaction modalities of these complexes been explored.…”

mentioning

confidence: 99%

Carbofunctionalization of Terminal Alkynes via Rhodium Catalysis Enabling Formations of Four Different Bonds

et al. 2023

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Described here is the oxygenative carbofunctionalization of terminal alkynes mediated by combined rhodium catalysis that enables regioselective quadruple formation of C−C, C−H, C−O, and C−heteroatom bonds. Mechanistic studies suggest that a disubstituted rhodium vinylidene complex is generated upon C−C bond formation at the terminal alkyne with tethered electrophiles such as alkyl halides, aldehydes, imines, and Michael acceptors. Subsequent intermolecular transfer oxygenation of the rhodium vinylidene with pyridine N-oxide generates a rhodium-complexed ketene intermediate that reacts with a variety of heteroatom nucleophiles to give rise to cyclic carboxylic acid derivatives.

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Ethynylglycine synthon, a useful precursor for the synthesis of biologically active compounds: an update. Part II: synthetic uses of ethynylglycine synthon

et al. 2018

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Metal Acetylides in Cycloaddition Reactions

Cited by 5 publications

References 65 publications

Copper and Silver Catalysis in the (3 + 2) Cycloaddition of Neutral Three-Atom Components with Terminal Alkynes

Copper and Silver Catalysis in the (3 + 2) Cycloaddition of Neutral Three-Atom Components with Terminal Alkynes

Carbofunctionalization of Terminal Alkynes via Rhodium Catalysis Enabling Formations of Four Different Bonds

Ethynylglycine synthon, a useful precursor for the synthesis of biologically active compounds: an update. Part II: synthetic uses of ethynylglycine synthon

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