Imination of Sulfur-Containing Compounds: XXXVI. A New Method of Synthesis and Oxidative Arylsulfonylimination of Sulfenamides

Koval, I. V.

doi:10.1007/s11178-005-0174-2

Cited by 2 publications

(1 citation statement)

References 13 publications

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“…10,[14][15][16][17][18][19][24][25][26][27] In elemento-organic chemistry oxidative imination of heteroatomic compounds, and mainly sulfur containing reagents, are of great significance. 1,2,[20][21][22] Divinyl sulfide is an important representative of practically useful sulfur organic compounds. The efficient method for the synthesis of divinyl sulfide was developed on the basis of acetylene and sodium sulfide, [28][29][30][31] which are available starting materials.…”

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confidence: 99%

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

Розенцвейг¹,

Rozentsveig²,

Levkovskaya³

et al. 2011

Arkivoc

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Section: Introductionmentioning

confidence: 99%

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

Розенцвейг¹,

Rozentsveig²,

Levkovskaya³

et al. 2011

Arkivoc

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AuBr₃-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

2009

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A new variant of the NO 2 -to-CO transformation (the Nef reaction) that occurs at room temperature under neutral conditions is uncovered. After the conversion of secondary nitroalkanes to phenylsulfenylketimines, these thiooximes are hydrolyzed quantitatively in situ, in THF-H 2 O at pH 7, by addition of AuBr 3 (but not with other MX n !). Adducts arising from asymmetric nitro-Michael and nitro-aldol reactions afford 1,4-diketones and r-alkoxy ketones, respectively, with full retention of the configuration of the stereocenters r to the CHNO 2 /CdN-SPh/CdO groups.Many reactions of gold compounds have been described in the past recent years. 1 Here we report an unexpected application of Au 3+ complexes, which we have incidentally discovered during a screening of inorganic salts in the search for optimum conditions for the hydrolysis of sulfenylketimines to ketones.The conversion of secondary nitro alkanes to ketones is a well-known useful reaction, which connects nitrogen and carbonyl chemistry. 2 Very recently, we developed a smooth protocol that takes place at room temperature (rt) without strong bases or acids; trimethylphosphine and an activator (ArSSAr, PySeSePy, or PhthN-SePh) were the only reagents required (Scheme 1). 3 In spite of the mild conditions, the procedure has the limitation that during the reduction of enantiopure nitro compounds, substituted at positions R to the CHNO 2 groups, racemic ketones were obtained, 3a as shown in the second equation of Scheme 1. Such a racemization occurs at the ketimine stage, via the enamines. 3a,4 To solve this handicap, we stopped the reduction cascade of nitro compounds (1) at sulfenylimines 2, by means of our protocol that uses PMe 3 and N-(phenylsulfenyl)phthalimide (PhthN-SPh) in THF at rt. 5 As indicated in Scheme 2, the key point was then to Res. 1974, 7, 281. Many methods are too harsh for our purposes (to be applied to NO 2 -containing polyfunctional fragments, in advanced steps of total syntheses). We have sometimes used an oxidative variant (2KHSO 5 ·KHSO 4 ·K 2 SO 4 , Oxone): (e) Ceccherelli, P.; Curini, M.; Marcotullio, M. C.; Epifano, F.; Rosati, O. Synth. Commun. 1998, 28, 3057. However, the necessity of having an alkaline aqueous medium to ensure the presence of nitronate ions and to make Oxone partially soluble, as well as the sensitivitity of several characteristic groups to peroxides, prevented us from using it in other cases. Lett. 1984, 25, 3707. (4) This would not be the case if the imine/enamine equilibrium would occur preferably via the CH 2 R′ moiety (e.g., for R′ ) Ar or EWG), but speaking in general the handicap was significant and restricted too much the application of our procedure.

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Imination of Sulfur-Containing Compounds: XXXVI. A New Method of Synthesis and Oxidative Arylsulfonylimination of Sulfenamides

Cited by 2 publications

References 13 publications

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

AuBr₃-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

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Imination of Sulfur-Containing Compounds: XXXVI. A New Method of Synthesis and Oxidative Arylsulfonylimination of Sulfenamides

Cited by 2 publications

References 13 publications

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

Unexpected reaction of N,N-dichloroarenesulfonamides with divinyl sulfide: formation of N-[2-chloro- and N-[2,2-dichloro-1-(arylsulfonylamino)ethyl]arenesulfonamides

AuBr3-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

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AuBr₃-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization