Methyl 3-Phenylsulfonyl-2-propenoate

(E)

[1865-13-0]  · C10H10O4S  · Methyl 3-Phenylsulfonyl-2-propenoate  · (MW 226.27) (Z)

[91077-67-7]

(used in Michael addition reactions;1 [2 + 2],2 [3 + 2],3 and [4 + 2]4,5 cycloadditions)

Physical Data: (E)-isomer mp 100 °C; (Z)-isomer mp 50.5-51.5 °C.

Solubility: (E)-isomer sol ethanol, methanol; (Z)-isomer sol chloroform, toluene; insol pentane.

Form Supplied in: both white crystalline solids.

Preparative Methods: methyl (E)-3-phenylsulfonyl-2-propenoate (1) is prepared in 70% yield by the reaction of Methyl Acrylate with benzenesulfonyl iodide followed by treatment with Triethylamine.3 Methyl (Z)-3-phenylsulfonyl-2-propenoate (2) is prepared in 88% yield by the Boric Acid mediated addition of Sodium Benzenesulfinate to Methyl Propiolate.5,6

Handling, Storage, and Precautions: potential alkylating and vesicant. Use in a fume hood.

Midhael Addition Reaction.

Methyl (E)-3-phenylsulfonyl-2-propenoate (1) has been reported to undergo Michael addition reactions with Pyrrolidine (eq 1), Sodium Methoxide (eq 2), and the morpholino enamine of cyclopentanone (eq 3) to produce, initially, b-substituted acrylates.1 In each case, attack of the nucleophile at the carbon a to the phenylsulfonyl group was followed by irreversible elimination of benzenesulfinic acid to give rise to the observed products.

Cycloaddition.

Methyl (E)-3-phenylsulfonyl-2-propenoate (1) undergoes [2 + 2] cycloaddition with N,N-Diethyl-1-propynylamine (eq 4) to provide regioselectively the corresponding tetrasubstituted cyclobutene in quantitative yield at 25 °C.2

[3 + 2] Cycloaddition.

It has been communicated that methyl (E)-3-phenylsulfonyl-2-propenoate (1) reacts with the nitrile imine generated in situ from phenylhydrazonyl chloride and triethylamine to afford a single regioisomeric 4,5-dihydropyrazole (eq 5) in 65% yield.3 The regioselectivity of this process was rationalized in terms of frontier orbital theory.

[4 + 2] Cycloaddition.

Heating methyl (Z)-3-phenylsulfonyl-2-propenoate (2) with a tricylic triene at 55-60 °C overnight results in the formation of the [4 + 2] cycloadduct in quantitative yield (eq 6).4 The latter cycloadduct was transformed into a quadricyclane derivative upon photolysis. Methyl (Z)-3-phenylsulfonyl-2-propenoate (2) also reacts with (E)-4-methylhexa-3,5-dien-1-ol in refluxing toluene to give the endo Diels-Alder adduct in 81% yield (eq 7).5 Interestingly, the ethyl ester analogous to methyl (E)-3-phenylsulfonyl-2-propenoate (1) reacts with this diene to give a quantitative yield of products derived from endo addition (eq 8), which have the opposite phenylsulfonyl regiochemistry to that observed with (2).


1. Benedetti, F.; Fabrissen, S.; Fagotto, R.; Risaliti, A. G 1990, 120, 613.
2. Eisch, J. J.; Galle, J. E.; Hallenbeck, L. E. JOC 1982, 47, 1608.
3. Chiericato, M.; Croce, P. D.; Cargnico, G.; Maiorana, S. JHC 1979, 16, 383.
4. (a) Paquette, L. A.; Kunzer, H. JACS 1986, 108, 7431. (b) Paquette, L. A.; Kunzer, H.; Kesselmayer, M. A. JACS 1988, 110, 6521.
5. Buss, A. D.; Hirst, G. C.; Parsons, P. J. CC 1987, 1836.
6. Hirst, A. D.; Parsons, P. J. OS 1990, 69, 169.

Simon Bailey

The Ohio State University, Columbus, OH, USA



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