Synthèse et réactivité des halogéno-2 sulfonyl-2 aziridines

Abstract

Clrit~rie Orgotritlrrc 2 , U.E.R. cles Scietlce.~ Estrcres er N n r r r r~l l c .~, Utlicer~sifc;tle B.P. 45, 63170 Aobiere, Frrrticc er Ecole Noriotrirle Srrpc;rirrrr.r rle Clrit?iie, 71 Borrlecco.tl CBre Bltrritr, 63000 Cler.t~ir)trf-Forr(~tr(I, Ft.trrrcr R e~u le 3 janvier 1979 JEAN-MARC GAILLOT, YVONNE GELAS-MIALHE et ROGER VESSIERE. Can. J. Chem. 57, 1958Chem. 57, (1979.Les halogtno-2 phCnylsulfonyl-2 aziridines sont obtenues par action du tetrahalogenure de carbone, en presence de potasse, sur les phCnylsulfonyl-2 aziridines.A partir des isopropylsulfonyl-2 aziridines, on obtient une monochloro et une dichloroaziridine; la reaction de Ramberg-Backlund n'est pas observee.Ces composCs haloginks se dCcomposent, soit thermiquement, soit en milieu acide, pour conduire aux a-halogCnoacetamides et a-phCnylsulfonylacCtamides N-substituks. Les halogtno-2 phCnylsulfony1-2 aziridines ne riagissent pas avec le cyanure de potassium ou le benzenethiolate de sodium. Elles sont reduites par le mtthylate, l'ethylate et I1Cthanethiolate de sodium, on obtient alors les phCnyIsulfony1-2 aziridines; le r61e du solvant est precise.JEAN-MARC GAILLOT, YVONNE GELAS-MIALHE, and ROGER VESSIERE. Can. J. Chem. 57,1958Chem. 57, (1979.Carbon tetrahalide reacts rapidly with 2-phenylsulfonyl aziridines in the presence of KOH, leading to 2-phenylsulfonyl 2-haloaziridines.Starting with 2-isopropylsulfonyl aziridines, a monochloro and a dichloroaziridine are produced; the Ramberg-Backlund reaction is not observed.These halo compounds decompose either thermally or in acidic medium leading to N-substituted a-haloacetamides and a-phenylsulfonylacetamides. 2-Phenylsulfonyl 2-haloaziridines are unreactive toward potassium cyanide or sodium thiophenoxide. Sodium methoxide, sodium ethoxide, or sodium thioethoxide reduce them to 2-phenylsulfonyl aziridines; the reaction depends upon the solvent.Dans un prCctdent mCmoire (1) nous avons dCcrit la priparation des phCnylsulfonyl-2 aziridines 1, 2 et 3 par action, dans le dimCthylsulfoxyde, d'une amine primaire sur une sulfone a-bromCe a,P-Cthy1Cnique. Par la suite, nous avons fait appel a ce procCdC pour accCder aux alkylsulfonyl-2 aziridines 4 et 5: Les phCnylsulfony1-2 aziridines 16, lc, 2b, 2det 3a traitCes par le tktrachlorure ou le tktrabromure de carbone en prCsence de potasse en poudre et d'alcool tert-butylique, conduisent, avec de bons rendements, aux halogeno-2 phCnylsulfony1-2 aziridines 6b, 6c, 7b, 7d, 8a, 9b, 9c, lob, 10d et l l a identifikes par leur analyse ClCmentaire et leur spectre de rmn (voir partie expkrimentale) :

Recent developments in Ramberg–Bäcklund and episulfone chemistry

“…We are also utilising the methodology for the synthesis of natural products such as sphingosine. However, treatment of bromovinyl sulfone 20 with amines did not produce the corresponding aziridines, as expected, 33 but generated allylamines 21 instead (Scheme 13).…”

Reaction of 4,5-Dichloro-1,2,3-dithiazolium Chloride with 2-(Phenylsulfonyl)acetonitrile

“…Subsequent attack by chloride on the disulfide group can lead to the stepwise migration of the phenylsulfone unit onto the sulfur via the spirocycle 19 and the formation of isothiazole 14. A few examples of such migrations leading to benzenesulfonothioates have been reported and include a thermal rearrangement of aziridines [29], a chlorotropic rearrangement [30] and a photochemical reaction of diphenyl sulfone [31]. The formation of isothiazole 14, which is a structural isomer of ylidene 13, is mechanistically interesting.…”

Methylc-1-cyano-t-2-methylsulfonyl-3-phenylcyclopropanecarboxylate

“…It is know, that some alpha-bromovinyl sulfones react with primary amines in DMSO to give the products of aza-Michael Ring Closure reaction (MIRCR) -2-sulfonylsubstituted aziridines (Galliot et al, 1979). Similarly MIRCR of phenyl-(Z)-(2-phenyl-2-chloroethenyl)sulfone with diethyl sodium malonate leads to formation of a sulfonylsubstituted cyclopropane (Yamamoto et al, 1985).…”