1-Hydroxymethyl-4-phenylsulfonybutadiene, a Versatile Building Block for the Synthesis of 2,3,4-Trisusbtituted Tetrahydrothiophenes

Dı́ez, David; Beneitez, M. Templo; Marcos, Isidro S.; Garrido, Narciso M.; Basabe, P.; Urones, Julio G.

doi:10.3390/90500323

Cited by 3 publications

(3 citation statements)

References 9 publications

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“…The asymmetric transition-metal-catalyzed epoxidation 105 of 1-hydroxymethyl-4-phenylsulfonylbutadiene 253 to the chiral substrate 254 was the starting step in the preparation of chiral nonracemic 2,3,4-trisubstituted tetrahydrothiophene compounds (Scheme 44). 106 Protection of 254 as the corresponding tosylate 255 and subsequent AlCl 3 -catalyzed oxirane ring-opening by acetone produced acetal 256. This compound was transformed into iodide 257, which provided a 6:4 mixture of tetrahydrothiophenes 258 and 259 by reaction with thiourea and hydrolysis of the intermediate thiouronium salt.…”

Section: 22mentioning

confidence: 99%

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

Benetti

Risi²,

Pollini³

et al. 2012

Chem. Rev.

100

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Section: 22mentioning

confidence: 99%

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

Benetti

Risi²,

Pollini³

et al. 2012

Chem. Rev.

100

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“…Recently, a renewed growing interest is observed towards the synthetic capabilities of 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes ( 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h , 1i , 1j ). This is because of their use in the synthesis of coenzyme Q 10 and of highly functionalizable 1‐arylsulfonyl 1,3‐dienes . The 4‐chloro‐2‐methyl‐1‐phenylsulfonyl‐2‐butene species is an intermediate in the synthesis of coenzyme Q 10 , and the latter dienes were found to react efficiently with aryl diazonium salts at the 3 and 4 positions .…”

Section: Introductionmentioning

confidence: 99%

“…Another method leading to a broad variety of 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes is represented as the Michael addition of nucleophiles to 1‐arylsulfonyl 1,3‐dienes . Earlier, we have developed an alternative method for preparing 1‐(arylsulfonyl)‐2‐ R ‐4‐chloro‐2‐butenes using arylation of conjugated dienes with aryl diazonium salts in the SO 2 saturated solution . In contrast to the previously developed methods, this protocol is very simple, relatively fast, and does not need expensive reactants or catalysts …”

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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Thiosugars: new perspectives regarding availability and potential biochemical and medicinal applications

Witczak

Culhane

2005

Appl Microbiol Biotechnol

112

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Thiosugars, containing a sulfur atom as heteroatom or a disaccharide linked via a sulfur bridge, possess unique physicochemical properties such as water solubility, which differs from conventional functionalized monosaccharides. The differences in biological activities between thiosugars and their oxygen analogs depend on geometric, conformational, and flexibility differences. They depend also on their electronic differences, the sulfide function being less electronegative and more polarizable than the ethereal moiety. Many functionalized thiosugars occur naturally and are potential targets for the development of carbohydrate-based therapeutics. Among the few new examples of the potential new targets are salacinol and kotalanol, tagetitoxin, thiolactomycin and analogues, mycothiol and analogues, and S-nitrosothiols. These new developments and representative examples of functionalized thiosugar prototypes as potential new targets are presented in this mini review.

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1-Hydroxymethyl-4-phenylsulfonybutadiene, a Versatile Building Block for the Synthesis of 2,3,4-Trisusbtituted Tetrahydrothiophenes

Abstract: A method to synthesize chiral 2,3,4-trisusbtituted tetrahydrothiophenes in both enantiomerically pure forms starting from 1-hydroxymethyl-4-phenylsulfonylbutadiene is described.

Cited by 3 publications

References 9 publications

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

Synthetic Routes to Chiral Nonracemic and Racemic Dihydro- And Tetrahydrothiophenes

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

Thiosugars: new perspectives regarding availability and potential biochemical and medicinal applications

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