Face selectivity in the photocycloaddition reactions of acrylonitrile to 5-substituted adamantan-2-ones and pyrolysis of the products to methyleneadamantanes

Wen-Sheng Chung*, Chia Chin Ho

*此作品的通信作者

研究成果: Article同行評審

5 引文 斯高帕斯(Scopus)

摘要

The photocycloaddition of acrylonitrile to 5-substituted adamantan-2-ones (1-X) produces two geometrically isomeric oxetanes in which the oxygen atom and the 5-substituent are in the anti or syn positions. The substituent was varied from fluoro, chloro, bromo, hydroxy to phenyl and the product ratios were similar (ca. 60:40) in all instances. Small portions (<5%) of the oxetanes were pyrolysed when analysed by GC at above 200 °C, and the products from the pyrolysis were confirmed to be the corresponding methyleneadamantanes by independent syntheses. Assignment of the configuration of the oxetanes was found to be consistent with 13C additivity scheme and the chemical shifts are more closely predicted using known oxetanes of 1-X with methacrylonitrile. The product formation bias resulting from the attack on the syn-face can be explained using the Cieplak transition state theory.

原文English
頁(從 - 到)553-557
頁數5
期刊Journal of the Chemical Society. Perkin Transactions 2
發行號3
DOIs
出版狀態Published - 1 三月 1997

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