m-chloroperbenzoic acid oxidation of 1,2-dithietes: First synthesis and characterization of 1,2-dithiete s-oxides and ethane-1,2-dithione S,S′-Dioxides (α-Disulfines)

Nakayama, Juzo; Mizumura, Ayako; Yokomori, Yoshinobu; Krebs, Adolf; Schütz, Karin E.

doi:10.1016/0040-4039(95)01834-5

Cited by 29 publications

(6 citation statements)

References 6 publications

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“…Atoms C3 and C4 of the adamantyl substituents are displaced from the dithiete mean plane by -0.091 (3) and 0.043 (3)A, respectively, resulting in a torsion angle C3--C1--C2--C4 of 7.4". This value contrasts with a similarly defined torsion angle of 84.4" in the structure of ring-opened 1,2-bis(1-adamantyl)ethane-1,2-dithione S,S'-dioxide, formed from this dithiete by oxidation with m-chloroperoxybenzoic acid (Nakayama et at., 1995). As shown, the adamantyl groups differ conformationally in that one is rotated slightly with respect to the other.…”

Section: Introductionmentioning

confidence: 71%

3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

Donahue¹,

Holm²

1998

Acta Crystallogr C

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The structure determination of 3,4-bis(1-adamantyl)-1,2-dithiete, (C10H15)2C2S2 or C22H30S2, reported herein is the first crystallographic characterization of a 1,2-dithiete molecule unsupported by a benzenoid frame. Two independent molecules exist in the asymmetric unit separated by a pseudo-inversion center. The S2C2 four-membered dithiete ring is planar, with a trapezoidal shape enforced by the longer disulfide bond [average 2.086 (2) A] compared with the olefinic bond [average 1.363 (6) A]. The adamantyl substituents differ from one another by adopting slightly different rotational conformations with respect to the dithiete ring. The quaternary C atoms of the adamantyl groups deviate only slightly from the plane of the dithiete ring (average displacement of 0.023 A).

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Section: Introductionmentioning

confidence: 71%

3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

Donahue¹,

Holm²

1998

Acta Crystallogr C

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“…K. Mechanistic Considerations Associated with Formation of 26. Compound ( Z , Z )- d , l - 26 , noteworthy as the first bis(thial S -oxide), bears a close relationship to the 2,3-dimethyl-1,4-butanedithial 1-oxides ( 21 ) postulated as intermediates in the rearrangement of 13 . We therefore propose that following oxidation of ( E , E )- 2 with 2 equiv of peracid, in the chairlike transition state for [3,3]-sigmatropic rearrangement, the vicinal sulfinyl oxygens of ( E , E )-bis(1-propenyl) vic -disulfoxide ( 28 ) can assume an anti geometry, suggested by theoretical calculations on an acyclic system to be favorable, , leading directly to ( Z , Z )- d , l - 26 (Scheme ).…”

Section: Resultsmentioning

confidence: 96%

Allium Chemistry: Synthesis and Sigmatropic Rearrangements of Alk(en)yl 1-Propenyl Disulfide S-Oxides from Cut Onion and Garlic¹

et al. 1996

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Reduction (LiAlH4) of propyl 1-propynyl sulfide (8) to (E)-1-propenyl propyl sulfide ((E)-10), C−S cleavage (Li/NH3) to lithium (E)-1-propenethiolate (Li (E)-11), and reaction with MeSO2Cl gives (E,E)-bis(1-propenyl) disulfide ((E,E)-2); i-Bu2AlH reduction of 8 to (Z)-10 and reaction with Li/NH3 and then MeSO2Cl gives (Z,Z)-2 via Li (Z)-11. Reaction of MeSO2SR (R = Me (12a), n-Pr (12b), CH2CHCH2 (12c), CHCHMe (12d)) with K (E)-11 gives (E,Z)-2 from (Z)-12d; Li (E,Z)-11 gives alkyl (E)- and (Z)-1-propenyl disulfides (MeCHCHSSR, R = Me (3a), n-Pr (3b), CH2CHCH2 (3c)) from 12a−c, respectively. Oxidation at −60 °C of (E,E)-, (Z,Z)-, and (E,Z)-2 gives (E)-1-propenesulfinothioic acid S-(E)-1-propenyl ester ((E,E)-13, (E,E)-MeCHCHS(O)SCHCHMe) from (E,E)-2, (Z,Z)-13 from (Z,Z)-2, and ca. 2:1 (E,Z)-13)/(Z,E)-13 from (E,Z)-2. Warming (Z,Z)-13 gives (±)-(1α,2α,3β,4α,5β)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (1a), endo-5-methyl-exo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14a), and exo-5-methyl-endo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14b). Warming (E,E)-13 gives 14a and 14b; (E,Z)-13/(Z,E)-13 gives (1α,2α,3α,4α,5β)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (1b), exo-5-methyl-exo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14c), and endo-5-methyl-endo-6-methyl-2-oxa-3,7-dithiabicyclo[2.2.1]heptane (14d). Oxidation of 3a−c gives MeCHCHSS(O)R (4) and MeCHCHS(O)SR (5). At −60 °C, m-CPBA (2 equiv) converts (E,E)-2 into (Z,Z)-d,l-2,3-dimethyl-1,4-butanedithial 1,4-dioxide (26) while (Z,Z)-2 gives meso- and d,l-26. With NaIO4, 4/5 (R = Me) gives (E)- or (Z)-12a and MeCHCHSO2SMe (6a); with m-CPBA (Z)-MeS(O)CHMeCHS+O- (25a) forms. At 85 °C 2 gives 1:1 cis- and trans-2-mercapto-3,4-dimethyl-2,3-dihydrothiophene (29).

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“…[41] These unusual α-disulfines 27 were also prepared by Schutz et al who generated them through oxidation of 1,2dithietes 26 and confirmed the structure using X-ray crystallography. [42] Scheme 11. Synthesis of disulfines from dithietes.…”

Section: Oxidation To Sulfinesmentioning

confidence: 99%

Generation, Reactivity and Uses of Sulfines in Organic Synthesis

et al. 2016

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This review focuses on the synthesis and reactivity of thioketone S‐oxides (sulfines). Sulfines have been long established as being reactive intermediates of high interest and with potential for wide application in organic synthesis. The review will cover many aspects of sulfines: the first section looks at the different routes to the synthesis of these compounds with a detailed look at more recently developed routes; the second section details the scope of reactivity of these types of compounds and how they are useful in synthetic organic chemistry with a particular look at cycloaddition and nucleophilic addition reactions.

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m-chloroperbenzoic acid oxidation of 1,2-dithietes: First synthesis and characterization of 1,2-dithiete s-oxides and ethane-1,2-dithione S,S′-Dioxides (α-Disulfines)

Cited by 29 publications

References 6 publications

3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

Allium Chemistry: Synthesis and Sigmatropic Rearrangements of Alk(en)yl 1-Propenyl Disulfide S-Oxides from Cut Onion and Garlic¹

Generation, Reactivity and Uses of Sulfines in Organic Synthesis

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m-chloroperbenzoic acid oxidation of 1,2-dithietes: First synthesis and characterization of 1,2-dithiete s-oxides and ethane-1,2-dithione S,S′-Dioxides (α-Disulfines)

Cited by 29 publications

References 6 publications

3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

3,4-Bis(1-adamantyl)-1,2-dithiete: the First Structurally Characterized Dithiete Unsupported by a Ring or Benzenoid Frame

Allium Chemistry: Synthesis and Sigmatropic Rearrangements of Alk(en)yl 1-Propenyl Disulfide S-Oxides from Cut Onion and Garlic1

Generation, Reactivity and Uses of Sulfines in Organic Synthesis

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Allium Chemistry: Synthesis and Sigmatropic Rearrangements of Alk(en)yl 1-Propenyl Disulfide S-Oxides from Cut Onion and Garlic¹