The preparation and photoreation of spiro(oxirane-2,6'-tricyclo(3.2.1.02,7)oct(3)en)-8'-ones. An intramolecular cycloaddition of photochemically generated ketene with the epoxide ring.

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概要

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• The oxidations of 1,5-dimethyl- and 1,3,5-trimethyl-6-methylenetricyclo[3.2.1.0<SUP>2,7</SUP>]oct-3-en-8-ones with 3-chloroperbenzoic acid or thallium(III) acetate resulted in the formation of 1′,5′-dimethyl and 1′,3′,5′-trimethylspiro[oxirane-2,6′-tricyclo[3.2.1.0<SUP>2,7</SUP>]oct[3]en]-8′-ones (<B>2a</B> and <B>2b</B>). The oxidation occured stereoselectively on the exocyclic double bond from the <I>exo</I>-side. The photochemical reactions of <B>2a</B> and <B>2b</B> resulted in the formation of 4,8-dimethyl- and 4,6,8-trimethyl-3,4-dihydro-1H-2-benzopyran-3-ones, both of which would be derived from an ene-type reaction of the ketene intermediate with the exoxide ring involved in the [4π+2σ] electronic system. The intermediacy of the ketene was assessed by low-temperature infrared spectroscopy as well as by a trapping experiment, the mechanistic pathways were confirmed by conducting the photoreaction in deuterated methanol.

• 公益社団法人 日本化学会の論文

著者

• Nitta Makoto

  Department Of Applied Pharmacology Toyama Medical And Pharmaceutical University

• Nakatani Hazime

  Department of Chemistry, School of Science and Engineering, Waseda University

• Omata Akihiko

  Department of Chemistry, School of Science and Engineering, Waseda University

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