Consecutive O−S/N−S Bond Cleavage in Gold‐Catalyzed Rearrangement Reactions of Alkynyl <i>N</i>‐Sulfinylimines

Tashiro, Hiroki; Terada, Masahiro; Nakamura, Itaru

doi:10.1002/anie.202100207

Cited by 7 publications

(4 citation statements)

References 80 publications

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“…Given the remarkable aptitude of functionalizations of alkynes to 2H-azirines, Nakamura et al [30] was among the first to demonstrate that the readily accessible alkynyl N-sulfinylimines could be transformed into corresponding 2H-azirines in the presence of [IPrAu(TAÀ Me)NTf 2 ] (Scheme 16). Sulfenyl and acyl groups could be introduced at the 3-position of the azirine ring through the consecutive cleavage of OÀ S and NÀ S bonds.…”

Section: Functionalization Of Alkyne To 2h-azirinementioning

confidence: 99%

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2H‐Azirines: Recent Progress in Synthesis and Applications

Xu,

Zeng,

Luo

et al. 2024

Eur J Org Chem

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2H‐arizines are important three‐membered heterocycles in organic chemistry. Recently, many advances in the synthesis and functionalization of 2H‐arizines have been reported. Neber rearrangement, isomerization of isoxazole, oxidation of enamine, C–H bond activation, decomposition of vinyl azide, functionalization of alkyne, and multi‐step synthesis have been developed for the efficient assembly of 2H‐azirines. As versatile and highly strained three‐membered unsaturated heterocycles, 2H‐azirines can be used as distinctive building blocks towards significant functional groups, and have attracted extensive attention for the fabrication of numerous heterocycles. Recent studies have focused on [3+n] ring‐expansion reactions, nucleophilic addition of C=N double bond or continuous nucleophilic addition followed by cyclization, ring‐opening of 2H‐azirines to acyclic compounds, and substitution of sp3‐C‐H of 2H‐azirines. One of the most critical challenges is seeking for a selective opening of the specific three bonds of the strained azirine circle, some of what can be achieved on the basis of metal catalyst, photocatalysis, or combination of metal catalyst and photocatalysis. In this review, recent advances involving the synthesis and reactivity of 2H‐arizines accompanied with challenges and breakthroughs are summarized. The review mainly covers the period from 2019 to 2023.

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Section: Functionalization Of Alkyne To 2h-azirinementioning

confidence: 99%

“…Given the remarkable aptitude of functionalizations of alkynes to 2H ‐azirines, Nakamura et al [30] . was among the first to demonstrate that the readily accessible alkynyl N ‐sulfinylimines could be transformed into corresponding 2H ‐azirines in the presence of [IPrAu(TA−Me)NTf 2 ] (Scheme 16).…”

Section: Synthesis Of 2h‐azirinesmentioning

confidence: 99%

2H‐Azirines: Recent Progress in Synthesis and Applications

Xu,

Zeng,

Luo

et al. 2024

Eur J Org Chem

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“…Transition-metal carbenes are versatile organometallic intermediates with metalcarbon double bonds, and studies of their structure–activity relationships and applications in organic synthesis have attracted significant interest . Over past decades, considerable attention has been focused on the generation of metal carbenes through the activation of CC bonds, mostly by late transition metals such as Au, Ag, Pt, Hg, Ir, Rh, and Pd . These transition metals further undergo a variety of transformations, including cyclopropanations, cycloadditions, rearrangements, C–H or X–H insertions, and carbene metathesis. − These reactions always occur in cascade transformations as inter- or intramolecular nucleophilic addition–elimination processes that deliver an α-oxo or α-imino metal carbene species (Scheme a).…”

Section: Introductionmentioning

confidence: 99%

“…Over past decades, considerable attention has been focused on the generation of metal carbenes through the activation of CC bonds, mostly by late transition metals such as Au, Ag, Pt, Hg, Ir, Rh, and Pd . These transition metals further undergo a variety of transformations, including cyclopropanations, cycloadditions, rearrangements, C–H or X–H insertions, and carbene metathesis. − These reactions always occur in cascade transformations as inter- or intramolecular nucleophilic addition–elimination processes that deliver an α-oxo or α-imino metal carbene species (Scheme a). However, there are few reports of the activation of alkynes by first-row metals to form the corresponding metal carbene species.…”

Section: Introductionmentioning

confidence: 99%

Cu(I)-Catalyzed Cross-Coupling Rearrangements of Terminal Alkynes with Tropylium Tetrafluoroborate: Facile Access to Barbaralyl-Substituted Allenyl Acid Esters and 7-Alkynyl Cycloheptatrienes

Fan

Pang

et al. 2022

J. Org. Chem.

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Herein, we report a novel strategy for the formation of copper carbene via the cycloisomerization of the π-alkyne–Cu(I) complex from terminal alkynes and tropylium tetrafluoroborate. Mechanistic studies and DFT calculations indicate that the reaction undergoes the intramolecular cycloisomerization process from the π-alkyne–Cu(I) complex to afford the copper carbene intermediate, followed by migratory insertion with the second terminal alkyne to afford the barbaralyl-substituted allenyl acid esters. In addition, we develop a mild and highly efficient Cu(I)-catalyzed cross-coupling protocol to synthesize 7-alkynyl cycloheptatrienes that has a broad functional group tolerance and is applicable to the late-stage functionalization of natural products.

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Lewis Acid Regulated Divergent Catalytic Reaction between Quinone Imine Ketals (QIKs) and 1,3‐Dicarbonyl Compounds: Switchable Access to Multiple Products Including 2‐Aryl‐1,3‐Dicarbonyl Compounds, Indoles, and Benzofurans

Chen

Deng

et al. 2021

Adv Synth Catal

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A catalytic Lewis acid regulated reaction between quinone imine ketals (QIKs) and 1,3-dicarbonyl compounds provides a divergent and tunable approach to a variety of skeletons, including a series of 2-aryl-1,3-dicarbonyl compounds, indoles, and benzofurans. The use of lithium chloride and ferrous bromide gives C3-or C2-alkylation products of the QIKs. The combination of ferrous bromide and trifluoromethanesulfonic acid delivers indole derivatives. Sequential hydrolysis and C3-alkylation occur in the presence of ytterbium (III) trifluoromethanesulfonate and stoichiometric amounts of water. When the reaction is performed with trifluoromethanesulfonic acid and stoichiometric amounts of water, benzofuran is obtained. This protocol utilizes mild conditions, exhibits regio-and chemoselectivity, and has broad functional group tolerance.

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Consecutive O−S/N−S Bond Cleavage in Gold‐Catalyzed Rearrangement Reactions of Alkynyl N‐Sulfinylimines

Cited by 7 publications

References 80 publications

2H‐Azirines: Recent Progress in Synthesis and Applications

2H‐Azirines: Recent Progress in Synthesis and Applications

Cu(I)-Catalyzed Cross-Coupling Rearrangements of Terminal Alkynes with Tropylium Tetrafluoroborate: Facile Access to Barbaralyl-Substituted Allenyl Acid Esters and 7-Alkynyl Cycloheptatrienes

Lewis Acid Regulated Divergent Catalytic Reaction between Quinone Imine Ketals (QIKs) and 1,3‐Dicarbonyl Compounds: Switchable Access to Multiple Products Including 2‐Aryl‐1,3‐Dicarbonyl Compounds, Indoles, and Benzofurans

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