Electrochemically-promoted synthesis of benzo[<i>b</i>]thiophene-1,1-dioxides <i>via</i> strained quaternary spirocyclization

Li, Rui-Tao; Yuan, Da-Fu; Ping, Meng-Qi; Zhu, Yu-Yi; Ni, Shao‐Fei; Li, Ming; Wen, Li‐Rong; Zhang, Linbao

doi:10.1039/d2sc01175a

Cited by 18 publications

(5 citation statements)

References 92 publications

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“…In particular, electrochemical C–X bond formation, such as C–S and C–O, has been a point of focus for the synthesis of useful compounds. However, there have been no reports on the electrochemical synthesis of sultone derivatives. , We have been interested in electrochemical synthesis, and during the course of our studies, we unexpectedly found that electrochemical oxidation of sulfonates efficiently afforded sultones via intramolecular dehydrogenative cyclization. Sulfonyl chlorides, which are stable and easy to handle, were excellent precursors for electrochemical sultone synthesis.…”

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confidence: 88%

Electrochemical Synthesis of Sultone Derivatives via Dehydrogenative C–O Bond Formation

Mitsudo,

Okumura,

Yohena

et al. 2023

Org. Lett.

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Electrochemical dehydrogenative C–O bond formation for the synthesis of sultones was achieved. In the presence of K2CO3 and H2O, constant current electrolysis of [1,1′-biphenyl]-2-sulfonyl chloride afforded an aryl-fused sultone quantitatively. Under the optimized conditions, a variety of sultone derivatives were obtained. Control experiments suggest that the electrochemical oxidation of the sulfonates generated in situ would afford sulfo radical intermediates.

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confidence: 88%

Electrochemical Synthesis of Sultone Derivatives via Dehydrogenative C–O Bond Formation

Mitsudo,

Okumura,

Yohena

et al. 2023

Org. Lett.

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“…Among them, a series of sulfonyl reagents, including sulfinic acids, sodium sulfinates, thiosulfonates, and DABCO·(SO 2 ) 2 , were employed as substrates. Very recently, sulfonyl hydrazides have been widely used as the green sulfonyl radical precursor via a dehydrazination with the release of environmentally friendly N 2 and H 2 as the byproducts in electrochemical organic synthesis . For example, Huang and co-authors demonstrated electrochemical radical sulfonylative oxycyclization of 2-vinyl benzamide for the construction of sulfonated 4 H -3,1-benzoxazines in 2020 (Scheme , eq 1) .…”

Section: Introductionmentioning

confidence: 99%

Access to Saturated Oxygen Heterocycles and Lactones via Electrochemical Sulfonylative Oxycyclization of Alkenes with Sulfonyl Hydrazides

et al. 2023

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A facile electrochemical sulfonylative cycloetherification of linear unsaturated alcohols with sulfonyl hydrazides under mild conditions has been accomplished. This catalyst-and oxidant-free protocol proceeds via electro-oxidation, followed by radical addition, as well as an intramolecular oxygen nucleophilic process. This methodology is compatible with a broad substrate scope and good functional group compatibility, which provides a valuable and convenient synthetic tool for the synthesis of saturated five-, six-, seven-, and eight-membered ring oxygen heterocycles. Furthermore, sulfonylative cycloesterification of linear unsaturated acids toward the lactone products has also been established under this electrochemical system. In addition, control experiments indicated that the N−H bonds of the sulfonyl hydrazide molecule are non-essential.

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“…The construction of 1,2,3-triazole rings is typically achieved through the click chemistry of heating or ultrasound-assisted or light-triggered [2 + 3] cycloaddition of alkynes/alkenes with organic azides that are catalyzed by organic metals, such as Cu(II) and Ag(I). − In addition, numerous synthetic methods have been developed for synthesizing triazoles, − such as the [3 + 2] cycloaddition of heterocyclic ketene aminals (HKAs)/ N,O -acetals with aryl azides …”

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confidence: 99%

Cycloaddition and Skeleton Rearrangement of Heterocyclic Ketene Aminals (HKAs) with 1-Diazonaphthalen-2(1H)-ones for the Synthesis of Functionalized 1,2,3-Triazoles

Zhao,

Qi,

et al. 2024

Org. Lett.

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We developed a protocol for the synthesis of highly functionalized 5,6-dihydro-imidazo[1,2-c][1,2,3]triazole derivatives 4−5 (DHITs) from 1-diazonaphthalen-2(1H)-one derivatives with heterocyclic ketene aminals (HKAs). This strategy involved cycloaddition and skeletal rearrangement entailing the heating of a mixture of substrates 1 with HKAs 2−3 and THF without any catalyst. As a result, a series of DHITs 4−5 were produced by cleaving one bond (1 C�N bond) and forming three bonds (1 N−N and 2 C−N bonds) in a single step. This protocol achieved the dual functionalization of diazo building blocks involving both the aromatic nitrogen alkylation reaction to form an ArC−N bond without any metal catalyst and the intermolecular cycloaddition of the N�N bond. These strategies can be used to synthesize functionalized DHITs for combinatorial and parallel syntheses via one-pot reactions without any catalyst.

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Electrochemically-promoted synthesis of benzo[b]thiophene-1,1-dioxides via strained quaternary spirocyclization

Abstract: We report an approach for the synthesis of benzothiophene motifs under electrochemical conditions by the reaction of sulfonhydrazides with internal alkynes. Upon the formation of a quaternary spirocyclization intermediate by...

Cited by 18 publications

References 92 publications

Electrochemical Synthesis of Sultone Derivatives via Dehydrogenative C–O Bond Formation

Electrochemical Synthesis of Sultone Derivatives via Dehydrogenative C–O Bond Formation

Access to Saturated Oxygen Heterocycles and Lactones via Electrochemical Sulfonylative Oxycyclization of Alkenes with Sulfonyl Hydrazides

Cycloaddition and Skeleton Rearrangement of Heterocyclic Ketene Aminals (HKAs) with 1-Diazonaphthalen-2(1H)-ones for the Synthesis of Functionalized 1,2,3-Triazoles

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