Synthesis of adamantane derivatives—43: 1,3-Dipolar cycloaddition reactivity of methyleneadamantane derivatives with substituted benzonitrile oxides |
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Authors: | Tadashi Sasaki Shoji Eguchi Toshiyuki Esaki Takanori Suzuki |
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Institution: | Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464, Japan |
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Abstract: | The 1,3-dipolar cycloaddition reactivity and regioselectivity of methyleneadamantane 1, ethyl adamantylideneacetate 7a, adamantylideneacetonitrile 7b and ω-methoxymethyleneadamantane 7c with substituted benzonitrile oxides 3a-i were calculated by CNDO/2 method using the perturbation equation derived by Klopman and Salem. The calculation predicted an exclusive formation of adamantan - 2 - spiro - 5' - 3' - aryl - Δ2' - isooxazoline 4a-i in the reactions of 1, 7a and 7b with 3a-i, and a formation of 67–69:33-31 mixture of 4a-i and isomeric 5a-i in the reaction of 7c with 3a-i. The predicted exclusive formation of 4a-i were experimentally observed in the reactions of 1,7a and 7b with 3a-i generated from 2a-i with Et3N or thermally, but the reaction of 7c with 3a did not afford the corresponding adducts. A considerably higher reactivity of CN triple bond than CC double bond was observed in the reaction of 7b with 3a and 1,2,4-oxadiazole derivative 11 was obtained as the major product. |
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