A one‐pot synthesis of alkynyl sulfides from terminal alkynes

Zheng, Weixin; Zheng, Fenfen; Hong, Yongmiao; Hu, Linfeng

doi:10.1002/hc.20744

Cited by 25 publications

(9 citation statements)

References 32 publications

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“…Attempts using 3‐buten‐1‐ol were unsuccessful, and the fact that 3‐buten‐1‐thiol is commercially not available made this approach difficult. However, based on a modified literature procedure, the synthesis of ortho ‐nitrophenyl thioynol ether 11 from trimethylsilyl alkyne 10 was attempted. To our surprise, 11 was not observed; instead, it underwent a spontaneous reaction towards polycycle 12 at room temperature (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

“…This cascade reaction has proven useful for the synthesis of nitrogen-containing spirocycles,but we intended to expand the scope to other heteroatom-containing compounds by starting from the corresponding ortho-nitrophenyl (thio)ynol ethers.Attempts using 3-buten-1-ol were unsuccessful, [16] and the fact that 3-buten-1-thiol is commercially not available made this approach difficult. However,b ased on am odified literature procedure, [17] the synthesis of ortho-nitrophenyl thioynol ether 11 from trimethylsilyl alkyne 10 was attempted. To our surprise, 11 was not observed;i nstead, it underwent as pontaneous reaction towards polycycle 12 at room temperature (Scheme 5).…”

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confidence: 99%

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Metal‐Free Cyclization ofortho‐Nitroaryl Ynamides and Ynamines towards Spiropseudoindoxyls

et al. 2018

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An efficient metal-free cascade reaction between 1-dibromovinyl-2-nitro-substituted arenes and secondary amines results in the formation of polycyclic pseudoindoxyls in a single step. The reaction mechanism leading to these fused ring systems was investigated, and is believed to involve the initial formation of nitroarylated ynamines/ynamides. These intermediates cycloisomerize towards N-alkenyl-tethered 2-aminoisatogens via a carbene intermediate as demonstrated by QTAIM (quantum theory of atoms in molecules) and ELF (electron localization function) analysis. A subsequent intramolecular dipolar cycloaddition afforded the title compounds.

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Section: Methodsmentioning

confidence: 99%

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confidence: 99%

Metal‐Free Cyclization ofortho‐Nitroaryl Ynamides and Ynamines towards Spiropseudoindoxyls

et al. 2018

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“…Following from our previous experience [ 7 ] with terminal acetylene thioethers, we now explore this reaction with alkynyl sulfides. In this regard 1a [ 13 ] was used as a model substrate and was treated with 50% HF·Py in dichloromethane. This, however, resulted in a very poor conversion (~10%) and gave a 4:1 product mixture of the fluorinated products 2a and 3a as illustrated in Scheme 1 .…”

Section: Resultsmentioning

confidence: 99%

Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers

Bello

O’Hagan

2015

Beilstein J. Org. Chem.

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A new method for the preparation of α-fluorovinyl thioethers is reported which involves the hydrofluorination of alkynyl sulfides with 3HF·Et 3 N, a process that requires Lewis acid activation using BF 3 ·Et 2 O and TiF 4 . The method gives access to a range of α-fluorovinyl thioethers, some in high stereoselectivity with the Z-isomer predominating over the E-isomer. The α-fluorovinyl thioether motif has prospects as a steric and electronic mimetic of thioester enols and enolates, important intermediates in enzymatic C-C bond forming reactions. The method opens access to appropriate analogues for investigations in this direction.1902

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“…A relatively inexpensive method for the synthesis of alkynyl thioethers was devised by Hu et al 45 who demonstrated that elemental sulfur could be reacted with deprotonated alkynes and the consequent alkynyl thiolates trapped with a range of electrophilies (Scheme 4.9).…”

Section: Scheme 48mentioning

confidence: 99%

The chemistry of ynol and thioynol ethers

Gray

Wilden

2016

Org. Biomol. Chem.

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Alkynyl ethers and alkynyl thioethers ('ynol ethers' and 'thioynol ethers') are appealing building-blocks in synthetic chemistry due to their ease of manipulation and predictable reactivity. Until recently however, their potential has remained underexploited due to difficulties in preparation and isolation. Although recent advances in synthetic chemistry have highlighted various applications for ynol ethers, the equivalent thioynol examples have been rather less exploited despite a unique and fascinating reactivity profile. Although superficially the chemistry of alkynyl ethers and their sulfide counterparts are similar, close examination of their chemistry reveals important differences which can be exploited by the synthetic chemist. This review will examine the preparation of both classes of compound and examine their reactivity to highlight their powerful synthetic applications. Particular focus will be made of thiynol ethers whose chemistry exhibits some fascinating differences compared to their oxygen counterparts and have immense untapped potential for synthetic chemistry.

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A one‐pot synthesis of alkynyl sulfides from terminal alkynes

Cited by 25 publications

References 32 publications

Metal‐Free Cyclization ofortho‐Nitroaryl Ynamides and Ynamines towards Spiropseudoindoxyls

Metal‐Free Cyclization ofortho‐Nitroaryl Ynamides and Ynamines towards Spiropseudoindoxyls

Lewis acid-promoted hydrofluorination of alkynyl sulfides to generate α-fluorovinyl thioethers

The chemistry of ynol and thioynol ethers

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