The Alkyne Zipper Reaction: A Useful Tool in Synthetic Chemistry

Sørskår, Åshild Moi; Stenstrøm, Helge Ø. K.; Stenstrøm, Yngve; Antonsen, Simen Gjelseth

doi:10.3390/reactions4010002

Cited by 3 publications

(3 citation statements)

References 142 publications

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“…33 The internal alkynes obtained via the cationic coupling process can be easily moved to the terminal position via the zipper reaction (Scheme 3B). 37 We found the procedure reported by Hoye 38 and co-workers particularly useful giving the desired product 27 in 94% yield. The terminal alkyne can then engage in many diverse reactions as illustrated by the synthesis of triazole 28, 39 iodo-olefin 29, 40 or arylated alkyne 30.…”

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confidence: 83%

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Al(III)-Promoted Formation of All-Carbon Quaternary Centers from Aliphatic Tertiary Chlorides and Alkynyl Silanes

Charki,

Müller

2024

J. Org. Chem.

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Despite the accessibility of numerous alkynes through coupling or substitution reactions, the synthesis of trialkyl-substituted alkynes is still a major challenge. Within this context, we reexplored the electrophilic alkynyl substitution between tertiary aliphatic chlorides and silylated alkynes. We were able to demonstrate that this approach is significantly more general than originally demonstrated by Capozzi and even tolerates several functional groups. Furthermore, we report diastereoselective reactions which in some instances gave excellent diastereoselectivity (dr >95:5).

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confidence: 83%

“…The internal alkynes obtained via the cationic coupling process can be easily moved to the terminal position via the zipper reaction (Scheme B) . We found the procedure reported by Hoye and co-workers particularly useful giving the desired product 27 in 94% yield.…”

mentioning

confidence: 94%

Al(III)-Promoted Formation of All-Carbon Quaternary Centers from Aliphatic Tertiary Chlorides and Alkynyl Silanes

Charki,

Müller

2024

J. Org. Chem.

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“…Upon isomerization, the integrity of a CC bond can be preserved by migration of the two mutually orthogonal π systems (“alkyne isomerization”; Figure , I → II and II → I ). Mechanistically, the formation of a transient allene intermediate is generally invoked to account for such processes. , Perhaps counterintuitively, the contra-thermodynamic isomerization of internal alkynes to terminal alkynes (often referred to as “alkyne zipper”) has been studied in detail and implemented in the synthesis of several complex structures (Figure A, isomerization “out”). , A particularly attractive feature of alkyne zipper reactions is their ability to sustain migration over long distances. Nonetheless, the strongly basic conditions employed severely limit functional group tolerance and impose to apply the method at early stages of multistep syntheses or necessitate additional protection/deprotection sequences.…”

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confidence: 99%

Remote Functionalization by Pd-Catalyzed Isomerization of Alkynyl Alcohols

Scaringi,

Leforestier,

Mazet

2024

J. Am. Chem. Soc.

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In recent years, progress has been made in the development of catalytic methods that allow remote functionalizations based on alkene isomerization. In contrast, protocols based on alkyne isomerization are comparatively rare. Herein, we report a general Pd-catalyzed long-range isomerization of alkynyl alcohols. Starting from aryl-, heteroaryl-, or alkyl-substituted precursors, the optimized system provides access preferentially to the thermodynamically more stable α,β-unsaturated aldehydes and is compatible with potentially sensitive functional groups. We showed that the migration of both π-components of the carbon−carbon triple bond can be sustained over several methylene units. Computational investigations served to shed light on the key elementary steps responsible for the reactivity and selectivity. These include an unorthodox phosphine-assisted deprotonation rather than a more conventional β-hydride elimination in the final tautomerization event.

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Reaction of acetylenic carbanions with C=N bond: dynamics of development, synthetic divergence, environmental safety

Schmidt,

Trofimov

2024

RUSS CHEM REV

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This review highlights dynamics of development and synthetic application of the recently discovered reaction of acetylenic carbanions, generated in superbase media, with C=N bond of different classes of substrates. A fundamental feature of this reaction is its synthetic divergence, i.e. its ability to proceed in various directions that manifests in novel transformations to selectively deliver (depending on structure of the acetylenes and substrates with C=N bond) structurally different synthetically important products. The review also discusses cascade processes, in which the key intermediates containing the C=N bond add acetylenes thereby participating in the self-organization of diverse and potentially useful compounds. The competitive advantage of the reaction and its daughter branches is environmental safety (neutrality), based on the fundamental chemical nature of these reactions as addition processes that occur without the release of by-products.<br> The bibliography includes 133 references.

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The Alkyne Zipper Reaction: A Useful Tool in Synthetic Chemistry

Cited by 3 publications

References 142 publications

Al(III)-Promoted Formation of All-Carbon Quaternary Centers from Aliphatic Tertiary Chlorides and Alkynyl Silanes

Al(III)-Promoted Formation of All-Carbon Quaternary Centers from Aliphatic Tertiary Chlorides and Alkynyl Silanes

Remote Functionalization by Pd-Catalyzed Isomerization of Alkynyl Alcohols

Reaction of acetylenic carbanions with C=N bond: dynamics of development, synthetic divergence, environmental safety

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