Vinylborane and vinylchalcogenide mediated synthesis of tri- and tetrasubstituted olefins from 1-alkynes

Gerard, Julien; Bietlot, Emerance; Hevesi, L.

doi:10.1016/s0040-4039(98)01938-8

Cited by 30 publications

(15 citation statements)

References 9 publications

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“…In 1965 Köster and Binger reported about the reaction of the sodium (alkynyl)triethylborates 1 with R 2 BCl electrophiles to yield the uniquely composed compounds 2 (Scheme ) . Their formation apparently involved a 1,2-ethyl group migration from boron to carbon.…”

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confidence: 99%

Facile 1,1-Carboboration Reactions of Acetylenic Thioethers

et al. 2013

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The acetylenic thioether PhSCCSPh undergoes a rapid 1,1-carboboration reaction with facile −SPh migration upon treatment with B(C 6 F 5 ) 3 to yield the borylated ketene dithioacetal product (PhS) 2 CC(C 6 F 5 )B(C 6 F 5 ) 2 (8a). The X-ray crystal structure analysis revealed an intramolecular sulfur−boron contact. The thioether PhCCSPh undergoes an analogous 1,1-carboboration reaction with B(C 6 F 5 ) 3 . The resulting vicinal S/B frustrated Lewis pair undergoes 1,2addition reactions to terminal acetylenes to give the respective zwitterionic six-membered heterocyclic sulfonium/borate products (all three examples were characterized by X-ray diffraction).

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confidence: 99%

Facile 1,1-Carboboration Reactions of Acetylenic Thioethers

et al. 2013

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“…Alkenyl sulfides have shown antibacterial activity, [23, 24] or alternatively participate in cross‐coupling reactions through C‐S cleavage [25, 26] . Achieving high regio‐ and stereoselectivity in previous synthetic approaches, however, remains challenging [27–31] . Alternative pinacolboration of thioacetylene precursors to make these compounds, for example, generally provides a mixture of regioisomers and requires a metal catalyst [31] .…”

Section: Figurementioning

confidence: 99%

“…[25,26] Achieving high regio-and stereoselectivity in previous synthetic approaches, however, remains challenging. [27][28][29][30][31] Alternative pinacolboration of thioacetylene precursors to make these compounds, for example, generally provides a mixture of regioisomers and requires a metal catalyst. [31] Electrophilic cyclization/group-transfer provides a potential solution to these challenges.…”

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confidence: 99%

Repurposing π Electrophilic Cyclization/Dealkylation for Group Transfer

et al. 2021

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A metal-free regio-and stereocontrolled grouptransfer route toward the synthesis of trisubstituted alkenes is described. In this route, an electrophilic heterocyclization is followed by ring-opening group transfer. Specifically, a thioboration reaction transforms readily available alkynyl sulfide precursors into alkenyl boronates and alkenyl sulfides with defined regio-and stereochemistry in one synthetic step using commercially available B-chlorocatecholborane (ClBcat). Mechanistic studies identified the likely pathway as proceeding through zwitterionic rather than haloborated intermediates. The regio-and stereochemistry set in the initial cyclization step is preserved in the final acyclic alkene product, producing alkenes with up to four modifiable substituents with predictable regio-and stereochemistry. Downstream functionalization reactions showcase the versatility of the substitutions of the resulting alkenes. The mechanistic concept maps onto future reaction designs, given the abundance of known electrophiles and nucleophiles for electrophilic heterocyclization/dealkylation sequences.

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“…The regio-and stereoselective synthesis of vinyl sulfides and selenides from simple alkynes via sulfur or selenium substituted vinyl boranes has been reported. 150 In addition, hydroboration of 1-phenylsulfanylalkynes was found to occur with high regioselectivity and the resultant 1-(phenylsulfanyl)alk-1-enylborane underwent Suzuki coupling to give vinyl sulfide products in moderate yield (Scheme 83). 150 The hydrozirconation of terminal alkynes and quenching of the intermediate alkenyl zirconium species with disulfides gives (E)-vinyl sulfides in good yield.…”

Section: Vinylic and Acetylenic Sulfides And Selenidesmentioning

confidence: 99%

“…150 In addition, hydroboration of 1-phenylsulfanylalkynes was found to occur with high regioselectivity and the resultant 1-(phenylsulfanyl)alk-1-enylborane underwent Suzuki coupling to give vinyl sulfide products in moderate yield (Scheme 83). 150 The hydrozirconation of terminal alkynes and quenching of the intermediate alkenyl zirconium species with disulfides gives (E)-vinyl sulfides in good yield. 151 Similarly, the hydrozirconation of alkynyl stannanes followed by quenching with arenesulfenyl chlorides gives (Z)-1arylsulfanyl vinyl stannanes (Scheme 84).…”

Section: Vinylic and Acetylenic Sulfides And Selenidesmentioning

confidence: 99%

The synthesis of thiols, selenols, sulfides, selenides, sulfoxides, selenoxides, sulfones and selenones

Procter¹

2000

J. Chem. Soc., Perkin Trans. 1

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Vinylborane and vinylchalcogenide mediated synthesis of tri- and tetrasubstituted olefins from 1-alkynes

Cited by 30 publications

References 9 publications

Facile 1,1-Carboboration Reactions of Acetylenic Thioethers

Facile 1,1-Carboboration Reactions of Acetylenic Thioethers

Repurposing π Electrophilic Cyclization/Dealkylation for Group Transfer

The synthesis of thiols, selenols, sulfides, selenides, sulfoxides, selenoxides, sulfones and selenones

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