Straightforward Synthesis of Strained α,β-Epoxysulfones via Epoxidation of Vinylsulfones Using N-Methylmorpholine N-Oxide as Epoxidizing Reagent

Rocío Rincón; Ana Aljarilla; María Criado; Joaquín Plumet

doi:10.1055/s-2007-984496

LETTER

Straightforward Synthesis of Strained α,β-Epoxysulfones via Epoxidation of Vinylsulfones Using N-Methylmorpholine N-Oxide as Epoxidizing Reagent

Rocío Rincón, Ana Aljarilla, María Criado, Joaquín Plumet*
Departamento de Química Orgánica I, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain
e-Mail: plumety@quim.ucm.es;

Abstract

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Abstract

An efficient, stereoselective route to the α,β-epoxysulfones using N-methylmorpholine N-oxide (NMO) as epoxidizing reagent is described.

Key words

vinylsulfone - α,β-epoxysulfone - N-methylmorpholine N-oxide - epoxidation

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Referenzen

References and Notes

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<A NAME="RG12807ST-10B">10b</A> interestingly, epoxidation of sulfone 14 with MCPBA (CH₂Cl₂, 20 °C, 4 h) provides the exo-epoxide 15 without the formation of Baeyer-Villiger oxidation product (Scheme 3). See: Prakash Rao HS. Murali R. Taticchi A. Scheeren HW. Eur. J. Org. Chem. 2001, 2869

<A NAME="RG12807ST-11">11</A> The exo selectivity in the nucleophilic additions and cycloadditions of the bicyclo[2.2.1]heptene double bond is a characteristic behavior of these compounds. For a comprehensive discussion, see: Huisgen R. Pure Appl. Chem. 1981, 53: 171 ; see in particular p. 181 and following

<A NAME="RG12807ST-12">12</A> Four isolated cases regarding the epoxidation reaction of α,β-unsaturated esters 16 with an amine oxide (NMO) to give endo-epoxides 17 (Scheme 4) have been previously described. See: Andres CJ. Spetseris N. Norton JR. Meyers AJ. Tetrahedron Lett. 1995, 36: 1613

Compounds 4 and 5 were synthesized by cycloaddition reaction of p-toluenesulfonylacetylene with furan and N-Boc pyrrole, respectively:

<A NAME="RG12807ST-13A">13a</A> Compound 4: Arjona O. Iradier F. Medel R. Plumet J. Heterocycles 1999, 50: 653

<A NAME="RG12807ST-13B">13b</A> Compound 5: Altenbach HJ. Blech B. Marco JA. Vogel E. Angew. Chem., Int. Ed. Engl. 1982, 21: 778

<A NAME="RG12807ST-13C">13c</A> See also: Chen Z. Trudell ML. Tetrahedron Lett. 1994, 35: 9649

In the same fashion, cycloaddition of cyclopentadiene and p-toluenesulfonylacetylene gave 6 in 99% isolated yield. Compound 7 (30% isolated yield) was prepared by trapping of isobenzofuran 22 [generated by reaction of 3,6-di(2′-pyridyl)-5-tetrazine(19) with 1,4-dihydro-1,4-endoxynaphthalene (20)] with p-toluene-sulfonylacetylene (Scheme [5] ). Analogous generation and trapping of N-Boc isoindole 23 gave compound 8 (62%). To the best of over knowledge these are the first cases concerning the application of the ‘tetrazine method’ to the synthesis of bicyclic α,β-unsaturated sulfones. Full details of the procedure will be reported in due course or upon request.

<A NAME="RG12807ST-13E">13e</A> For the generation of isobenzofuran, see: Warrener RN. J. Am. Chem. Soc. 1971, 93: 2346

<A NAME="RG12807ST-13F">13f</A> For the generation of N-Boc isoindole, see: Priestly GM. Warrener RN. Tetrahedron Lett. 1972, 4295

Typical Experimental Procedure: To a solution of compounds 4-8 (0.43 mmol) in anhyd CH₂Cl₂ (6 mL), NMO (0.86 mmol) was added in one portion under argon at 0 °C. The mixture was allowed to react at r.t. during 24 h. After this time the solvent was removed under reduced pressure and the residual material was purified by column chromatography (hexane-EtOAc, 4:1).