Reaction of methanesulfonyl nitrene with benzene. Attempts to generate sulfonyl nitrenes from sources other than the azides

Abramovitch, R. A.; Bailey, Thomas D.; Takaya, Takao; Uma, V.

doi:10.1021/jo00917a013

Cited by 73 publications

(45 citation statements)

References 7 publications

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“…To produce imidoiodinanes, iodosobenzene and iodosobenzene diacetate react with sulfonamides. [9,34] As mentioned before, the initial step is presumably the solvolysis of the initial iodine reagent. [19] Sulfonamides react by nucleophilic substitution on the iodine atom, possibly giving birth to a dissociated intermediate arising from the IÀO bond cleavage on A. Deprotonation eventually delivers the iminoiodinanes (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Leca

Song

Amatore

et al. 2004

Chemistry A European J

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Reaction of sulfonamides with iodosobenzene leads to phenyliodinanes. A new catalysis reaction of the decomposition of these products in the presence of sulfoxides that allows the smooth synthesis of sulfoximines has been evidenced and studied: copper(II) salts were used to prepare compounds 4 a-j and 5 b, d, f, j, k from the corresponding, easily prepared, sulfoxides. The reactions proceed with retention of configuration at the sulfur center, and copper(II) triflate is the best candidate for the catalyst for the imination. Switching from sulfonamides to sulfinamides in the preparation of the starting iodinanes completely alters the reaction pathway: iodinanes are no longer accessible, and sulfonimidates 7 a-j are obtained instead. This behavior can be rationalized by the increase in pK(a) brought about by the removal of one oxygen atom from the sulfur center. Sulfonimidates are interesting molecules with varied applications. Optimization of their one-pot synthesis has been achieved by carrying out the reaction in acetonitrile. The stereochemical study has shown that the transformation proceeds with global retention of the configuration at the sulfur center, albeit with erosion of the enantiomeric purity. A model accounting for this outcome is proposed. In addition, the presence of oxidized sulfonamide by-products has been explained, and this latter pathway becomes the sole one when alcohol is replaced by water. Good yields of the oxidized products are obtained.

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Section: Resultsmentioning

confidence: 99%

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Leca

Song

Amatore

et al. 2004

Chemistry A European J

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“…Ρage 131 ©ARKAT USA, Inc 4 Si as internal standard. Thin-layer chromatography was performed on Merck silica gel 60 plates with a fluorescent indicator.…”

Section: Issn 1551-7012mentioning

confidence: 99%

“…N-(9-phenyl-9H-fluoren-9-yl)amino-3-[N-(2-trimethylsilyl-ethanesulfonyl)aziridin-2′-yl]propanoate (13). To a suspension of activated 3Å molecular sieves (3.75 g) in acetonitrile (25 mL) were successively added compound 10 (2.39 g, 5.8 mmol) and Cu(CH 3 CN) 4 PF 6 (0.63 g, 0.25 eq.). A mixture of 2-trimethylsilylethanesulfonamide (1.37 g, 1.3 eq.)…”

Section: Issn 1551-7012mentioning

confidence: 99%

“…By contrast, the aza-analogues of 1, i.e. the iminoiodanes or the iodonium imides of general formula ArI=NSO 2 R, remained unknown until their preparation was described in the mid 70's by Abramovitch 4 and, particularly, by Yamada. 5 Nearly two more decades were necessary before these reagents were shown to be synthetically useful for C-N bond formation.…”

Section: Introductionmentioning

confidence: 99%

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Copper-catalyzed aziridination of allylglycine derivatives

Leman¹,

Sanière²,

Dauban³

et al. 2003

Arkivoc

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“…However, it suffered several shortcomings. Owing to the requirement of aromatic sulfonamides as precursors for the phenyliodinanes [5], the possibilities of carrying out intramolecular aziridinations and/or amidations [6] appeared very limited. In addition, a large excess of substrate was necessary in the case of intermolecular reactions to achieve satisfactory yields, while reactions carried out with an excess of reagent over the substrate produced unsatisfactory results.…”

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confidence: 99%

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

Fruit

Müller

2004

Helvetica Chimica Acta

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Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc) 2 and MgO in high yields and with enantioselectivities of up to 66% (Scheme 3, Table 1 isoquinoline-2-acetato). In addition, these carboxylatodirhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).Introduction. ± Amidation of saturated CÀH bonds and aziridination of olefins catalyzed by metal complexes based on Fe, Mn, Ru, Cu, or Rh are established methodologies for CÀN bond-formation [1] and, consequently, for the synthesis of amine derivatives. Some years ago, the Rh II -catalyzed aziridination [2] and sulfonamidation [3] with phenyliodinanes derived from aromatic sulfonamides has been investigated in our group. The reactions exhibited features analogous to the corresponding metal-catalyzed carbene-transfer reactions [4]. The aziridination was found to be stereospecific, except in the case of stilbene, and the amidation proceeded with retention of configuration at the reacting C-atom, indicating intervention of a metal-complexed nitrene, in analogy to the corresponding intermediate metallocarbenes resulting from decomposition of diazo compounds with Rh II catalysts. Some preliminary experiments showed that the system was suitable for asymmetric nitrene transfer. However, it suffered several shortcomings. Owing to the requirement of aromatic sulfonamides as precursors for the phenyliodinanes [5], the possibilities of carrying out intramolecular aziridinations and/or amidations [6] appeared very limited. In addition, a large excess of substrate was necessary in the case of intermolecular reactions to achieve satisfactory yields, while reactions carried out with an excess of reagent over the substrate produced unsatisfactory results. Finally, some reactions, in particular intermolecular amidations, proceeded very sluggishly and resulted in decomposition of the phenyliodinanes to afford sulfonamides without generation of the expected products of nitrene insertion.The transition-metal-catalyzed nitrene transfer has been further developed by other groups. Dodd, Dauban, and co-workers reported that, contrary to the traditional opinion [7], phenyliodinanes derived from aliphatic sulfonamides are isolable and may be used for nitrene-transfer reactions [8]. In addition, they found conditions allowing

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Reaction of methanesulfonyl nitrene with benzene. Attempts to generate sulfonyl nitrenes from sources other than the azides

Cited by 73 publications

References 7 publications

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Copper-catalyzed aziridination of allylglycine derivatives

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

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