Cycloaddition Reactions of 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne

• Published in: Journal of organic chemistry Vol. 64; no. 20; pp. 7426 - 7432
• Main Authors: Back, Thomas G, Bethell, Richard J, Parvez, Masood, Taylor, Jerry A, Wehrli, Daniel
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.10.1999; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; ANTI-MICHAEL; DIELS-ALDER REACTIONS; VINYL SULFONES; ADDITION REACTIONS; 1-(PHENYLSELENO)-2-(P-TOLUENESULFONYL)ETHYNE; KEY INTERMEDIATE; EPIBATIDINE; TRIMETHYLSILYLMETHYL AZIDE; ACETYLENE EQUIVALENT; BETA-(PHENYLSELENO)VINYL SULFONES
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo990730t

1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (1) is an effective dienophile and dipolarophile. It underwent facile Diels−Alder reactions with a variety of dienes to afford vicinal sulfone- and selenide-functionalized 1,4-cyclohexadienes. Unexpected regiochemistry that is the opposite of what is obtained with simple acetylenic sulfones was observed with several unsymmetrical dienes containing methyl or methoxy substituents at the 1- or 2-position. Acetylene 1 reacted with (trimethylsilyl)methyl azide, diazomethane, and 2,4,6-trimethylbenzonitrile N-oxide via 1,3-dipolar cycloadditions to afford the corresponding triazole, 1,2-diazole, and isoxazole products. It also underwent an ene reaction with β-pinene that showed anomalous regiochemistry compared to other acetylenic sulfones. The Diels−Alder cycloadducts obtained from the reaction of 1 with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were readily converted into the corresponding β-keto sulfones and ketones, thus rendering 1 as the synthetic equivalent of p-toluenesulfonylketene and ketene, respectively. Base-catalyzed elimination of TsOH from the Diels−Alder cycloadduct obtained with 2,3-dimethyl-1,3-butadiene afforded the corresponding aryl phenyl selenide, while the adduct from piperylene underwent oxidation to its selenoxide, followed by a Pummerer-type reaction to produce 2-(phenylseleno)-3-(p-toluenesulfonyl)toluene. The reaction of the bicyclic Diels−Alder product obtained from 1,3-cyclohexadiene with MeCu(SePh)Li resulted in substitution of the phenylseleno moiety by a methyl group, whereas similar treatment of the monocyclic adduct derived from piperylene effected elimination of PhSeH and aromatization.