Stereoselective Addition of Arene Thiols to 1,4-Disubstituted-2-Butynes

Thyagarajan, B. S.; Wood, B. F.; Swynnerton, Nollie F.

doi:10.1080/03086648508077679

Cited by 6 publications

(1 citation statement)

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“…Although some of the presented reactions are not principally new, we propose synthetic procedures that are much faster, cheaper, and simpler than the previously developed synthesis. The described computational approach will be useful for studying chemical reactivity in the electrophile–nucleophile reactions of 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes, 1‐arylsulfonyl 1,3‐dienes, and the related compounds …”

Section: Introductionmentioning

confidence: 99%

A combined experimental and density functional study of 1-(arylsulfonyl)-2-R-4-chloro-2-butenes reactivity towards the allylic chlorine

Bondarchuk

Smalius

Minaev

2015

J. Phys. Org. Chem.

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Nucleophilic substitution and dehydrochlorination reactions of a number of the ring-substituted 1-(arylsulfonyl)-2-R-4-chloro-2-butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1-arylsulfonyl 1,3-butadienes (48-95%), 1-(arylsulfonyl)-2-R-4-(N,N-dialkylamino)-2-butenes (31-53%), 1-(arylsulfonyl)-2-R-2-buten-4-ols (37-61%), and bis[4-(arylsulfonyl)-3-R-but-2-enyl]sulfides (40-70%). The density functional theory B3LYP/6-311++G(2d,2p) calculations of the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and hyperconjugation by the SO 2 Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic moiety display a high correlation (R 2 > 0.97) with the Hammett (σ p ) constants. 1-Arylsulfonyl 1,3-butadienes are characterized by a partly broken π conjugated system, which follows from analysis of the two-centered delocalization (δ) and localization (λ) index values. The highest occupied molecular orbital energies of 1-arylsulfonyl 1,3-butadienes are lower than those of 1,3-butadiene explaining their low reactivity towards the Diels-Alder condensation.

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Section: Introductionmentioning

confidence: 99%