Nucleophilic substitution at dicoordinated sulfur. Effect of the leaving group on the reaction between triphenylmethyl sulfenyl derivatives and butylamine

Ciuffarin, Ennio; Guaraldi, Giancarlo

doi:10.1021/jo00831a063

Cited by 39 publications

(11 citation statements)

References 3 publications

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“…No solid precipitated running the reaction in dry ether or ether/pentane. However, n ‐butylamine was reactive towards triphenylmethyl sulfenyl iodide34 and the sterically protected aromatic sulfenyl iodides reacted with excess benzylamine giving sulfenamides 29…”

Section: Resultsmentioning

confidence: 99%

The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As‐S‐I

Ioannou

Vachliotis

Chrissanthopoulos

2015

Zeitschrift anorg allge chemie

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Bunsen's cacodyl disulfide, Me2As(S)‐S‐AsMe2 (1), reacted with iodine giving the novel dimethylarsinosulfenyl iodide, Me2As‐S‐I (3) although theoretical calculations indicated that the AsV compound Me2As(S)‐I (4) was more stable in the gas phase. The oily product was stable neat and as a solution in CDCl3 at +4 °C and –20 °C for at least 15 d. Light, H2O, H2O2, and Zn dust, but not NaI or Ag, decomposed it. Compound 3 did not interact with Ph3N, with Ph2NH and PhNH2 it interacted but not reacted. 3 was decomposed by piperidine, with pyridine and 4‐dimethylaminopyridine it interacted and produced Me2As‐SS‐AsMe2 (2) and I2 that formed charge transfer complexes Base·I2, whereas Et3N decomposed 3, and 3Et3N·2I2 was isolated. 3 was desulfurized by Ph3P and (Me2N)3P completely, and by (PhO)3P and (PhS)3P partially. The reactions of 3 with (Me2N)3P, (PhS)3P, and (EtO)3P were complicated. From the AsIII nucleophiles, only Ph3As was bound, while (PhS)3As reacted slowly in a complicated manner with 3. No interaction of 3 with MeOH or PhOH was observed but NaOH, Ag2O, and PhONa decomposed it. Thiophenol produced traces of Me2As‐SPh (10) and sodium thiophenolate attacked mainly at AsIII of 3. Thus, externally stabilized sulfenium ions of the type Me2As‐S‐Nu+I– were not obtained.

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Section: Resultsmentioning

confidence: 99%

The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As‐S‐I

Ioannou

Vachliotis

Chrissanthopoulos

2015

Zeitschrift anorg allge chemie

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“…A sulfur atom is usually present in a divalent state in organic molecules. However, it sometimes adopts a weak coordination to a proximate heteroatom (X), such as O, N, and S, in solution as well as in the solid state [ 1 , 2 , 3 , 4 ]. Such hypervalent weak atomic interactions, so-called nonbonded S···X interactions, are of significant interest because they can control not only the molecular assembly of organic sulfur compounds in advanced materials with unique conductivity or optical properties [ 5 , 6 ] but also the structure and reactivity of isolated molecules [ 7 , 8 , 9 ].…”

Section: Introductionmentioning

confidence: 99%

Hypervalent Nonbonded Interactions of a Divalent Sulfur Atom. Implications in Protein Architecture and the Functions

2012

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In organic molecules a divalent sulfur atom sometimes adopts weak coordination to a proximate heteroatom (X). Such hypervalent nonbonded S···X interactions can control the molecular structure and chemical reactivity of organic molecules, as well as their assembly and packing in the solid state. In the last decade, similar hypervalent interactions have been demonstrated by statistical database analysis to be present in protein structures. In this review, weak interactions between a divalent sulfur atom and an oxygen or nitrogen atom in proteins are highlighted with several examples. S···O interactions in proteins showed obviously different structural features from those in organic molecules (i.e., πO → σS* versus nO → σS* directionality). The difference was ascribed to the HOMO of the amide group, which expands in the vertical direction (πO) rather than in the plane (nO). S···X interactions in four model proteins, phospholipase A2 (PLA2), ribonuclease A (RNase A), insulin, and lysozyme, have also been analyzed. The results suggested that S···X interactions would be important factors that control not only the three-dimensional structure of proteins but also their functions to some extent. Thus, S···X interactions will be useful tools for protein engineering and the ligand design.

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“…4 The only structural analysis of a sulfenyl iodide was carried out for Ph 3 CSI at 2118 °C, 5 which is stable in the solid state at 278 °C and in solution in the dark. 6 Thus, no sulfenyl iodide stable at room temperature has so far been structurally characterized. 7 On the other hand, the reported value of the S-I bond dissociation energy is not so small (49.4 ± 2 kcal mol 21 for HS-I), 8 suggesting that this species will be stable if the disproportionation process is suppressed.…”

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confidence: 99%

Synthesis and crystal structure of an arenesulfenyl iodide with unprecedented stability

Goto¹,

Holler²

1998

Chem. Commun.

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Nucleophilic substitution at dicoordinated sulfur. Effect of the leaving group on the reaction between triphenylmethyl sulfenyl derivatives and butylamine

Cited by 39 publications

References 3 publications

The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As‐S‐I

The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As‐S‐I

Hypervalent Nonbonded Interactions of a Divalent Sulfur Atom. Implications in Protein Architecture and the Functions

Synthesis and crystal structure of an arenesulfenyl iodide with unprecedented stability

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Nucleophilic substitution at dicoordinated sulfur. Effect of the leaving group on the reaction between triphenylmethyl sulfenyl derivatives and butylamine

Cited by 39 publications

References 3 publications

The Reaction of Bunsen's Cacodyl Disulfide, Me2As(S)‐S‐AsMe2, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me2As‐S‐I

The Reaction of Bunsen's Cacodyl Disulfide, Me2As(S)‐S‐AsMe2, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me2As‐S‐I

Hypervalent Nonbonded Interactions of a Divalent Sulfur Atom. Implications in Protein Architecture and the Functions

Synthesis and crystal structure of an arenesulfenyl iodide with unprecedented stability

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Product

Resources

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The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As‐S‐I

The Reaction of Bunsen's Cacodyl Disulfide, Me₂As(S)‐S‐AsMe₂, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide, Me₂As‐S‐I