[101933-29-3]  · C8H7NO4S  · 1-Nitro-2-phenylsulfonylethylene  · (MW 213.23)

(Michael acceptor;3-5 acetylene equivalent in the Diels-Alder reaction8,9)

Alternate Name: 1-phenylsulfonyl-2-nitroethylene.

Physical Data: mp 148-150 °C.

Solubility: sol THF, Et2O, CHCl3, CH2Cl2.

Analysis of Reagent Purity: IR 1160, 1350, 1550 cm-1; NMR d 7.50-7.96.

Preparative Method: by oxidation of 1-Nitro-2-phenylthioethylene with m-Chloroperbenzoic Acid (2 equiv).2

Michael Acceptor.

Addition-elimination reactions of various nucleophiles to this reagent provide a useful method for the preparation of various 1-nitroalkenes. Polyfunctional organozinc and copper reagents react with this reagent to give polyfunctional 1-nitroalkenes. Organometallics bearing an ester (eq 1),3 diene (eq 2),4 or oxygen function (eq 3)5 give terminal nitroalkenes substituted with these functional groups. Thus a precursor for an intramolecular Diels-Alder reaction and new allylic acetates bearing terminal nitroalkenes are readily prepared by this procedure.

Acetylene Equivalent.

This reagent is an excellent dienophile in the Diels-Alder reaction and reacts with various dienes to give the adducts under mild conditions. Subsequent treatment of the resulting b-nitro sulfones with Tri-n-butylstannane results in the reductive elimination of the nitro and sulfonyl groups6 to give 1,4-cyclohexadienes. Thus this reagent serves as a very reactive Acetylene equivalent,7 and various dienes have been converted into 1,4-cyclohexadienes by this procedure (eqs 4 and 5).8,9

1. (a) Ono, N.; Kaji, A. S 1986, 693 (b) Ono, N. Nitro Compounds : Recent Advances in Synthesis and Chemistry; Feuer, H.; Nielsen, A. T., Eds.; VCH: New York, 1990; p 1.
2. Ono, N.; Kamimura, A.; Kaji, A. JOC 1986, 51, 2139.
3. Jubert, C.; Knöchel, P. JOC 1992, 57, 5425.
4. Jubert, C.; Knöchel, P. JOC 1992, 57, 5431.
5. Knöchel, P.; Chou, T. S.; Jubert, C.; Rajagopal, D. JOC 1993, 58, 588.
6. Ono, N.; Miyake, H.; Hamamoto, I.; Tamura, R.; Kaji, A, CL 1981, 1139.
7. De Lucchi, O.; Modena, G. T 1984, 40, 2585.
8. Ono, N.; Kamimura, A.; Kaji, A. JOC 1988, 53, 251.
9. Danishefsky, S.; Lee, J. Y. JACS 1989, 111, 4829.

Noboru Ono

Ehime University, Matsuyama, Japan

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