A Novel Synthesis of Allyl Sulfides by Organosamarium Reagents†

Zhan, Zhuang‐Ping; Zhang, Yongmin

doi:10.1039/a706725i

Cited by 5 publications

(1 citation statement)

References 15 publications

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“…Perhaps the samarium powder was activated by I 2 and aqueous NH 4 Cl [16b,18], thus an electron was transferred to the substrate 2 to form the radical SCHEME 4 anion 7 [19]; when R was an alkyl group, selective cleavage of the S S bond occurred to form S-radical intermediate 8, which then dimerized to afford the di(Z-allyl) disulfide 5; but when R was an aryl group, cleavage of the C S bond may be predominated to give allyl radical species 9 or 10. Then, 9 received another electron from Sm to produce allyl anion intermediate 11.…”

Section: Synthesis Of Symmetrical Diallyl Disulfides or Methyl Cinnammentioning

confidence: 99%

Stereoselective synthesis of trisubstituted alkenes containing (Z)‐allylthio units from the acetates of Baylis–Hillman adducts

Liu

et al. 2008

Heteroatom Chemistry

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Section: Synthesis Of Symmetrical Diallyl Disulfides or Methyl Cinnammentioning

confidence: 99%

Stereoselective synthesis of trisubstituted alkenes containing (Z)‐allylthio units from the acetates of Baylis–Hillman adducts

Liu

et al. 2008

Heteroatom Chemistry

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ChemInform Abstract: A Novel Synthesis of Allyl Sulfides by Organosamarium Reagents.

Zhan¹,

Zhang²

1999

ChemInform

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New synthetic route to modafinil drug including desulfobenzhydrylation of sodium carbamoylmethyl thiosulfate: experimental and quantum chemical studies

et al. 2010

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A new synthetic route to 2 benzhydrylsulfinylacetamide (1), a nootropic drug modafinil, is described. The synthesis includes the alkylation of sodium thiosulfate with chloroacetamide to sodium carbamoylmethyl thiosulfate, the desulfobenzhydrylation of the latter by benzhydrol in formic acid to form benzhydrylthioacetamide (3a), and the further oxidation of this thioamide with hydrogen peroxide. According to B3LYP/6 31G** DFT calculations, the key step of the synthesis, namely, desulfobenzhydrylation of salt 6a, occurs only insignificantly due to the energetically unfavorable direct attack of this salt by benzhydryl formate; the reaction mainly involves the attack by the benzhydrilium carbocation Ph 2 CH + . The oxidation of sulfide 3a to sulfinylacetamide 1 is efficiently catalyzed by side proton donor molecules (constituents of the transition states of the reaction). The oxidant can be the anionic form of the reactant (HO 2 -ion), which reacts with sulfide 3a via the unusual noncatalytic mechanism. At the step of transition state formation, this mechanism resembles the S N 2 substitution.

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A Novel Synthesis of Allyl Sulfides by Organosamarium Reagents†

Abstract: Organosamarium reagents react with sodium alkyl thiosulfates to afford allyl sul®des; a reaction mechanism involving organosamarium(II) and organosamarium (III) intermediates is suggested.

Cited by 5 publications

References 15 publications

Stereoselective synthesis of trisubstituted alkenes containing (Z)‐allylthio units from the acetates of Baylis–Hillman adducts

Stereoselective synthesis of trisubstituted alkenes containing (Z)‐allylthio units from the acetates of Baylis–Hillman adducts

ChemInform Abstract: A Novel Synthesis of Allyl Sulfides by Organosamarium Reagents.

New synthetic route to modafinil drug including desulfobenzhydrylation of sodium carbamoylmethyl thiosulfate: experimental and quantum chemical studies

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