Face selectivity in the Paterno-Büchi reactions of methacrylonitrile to 5-substituted adamantan-2-ones

Wen-Sheng Chung*, Yei De Liu, Nae Jean Wang

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

The photocycloaddition of methacrylonitrile to 5-substituted adamantan-2-ones (1-X) produces two geometrically isomeric oxetanes in which the oxygen atom and the 5-substituent are in anti or syn positions. The substituent was varied from fluoro, chloro, bromo, phenyl to SiMe 3 and the product ratios, except for SiMe 3 , were similar (ca. 56:44) in all instances. Structure determination of the anti and syn oxetanes were carried out by 1 H and 13 C NMR and mass spectroscopy. The structure of syn-5-bromospiro[adamantane-2,2′-oxetane] (syn-5-Br) was further supported by single-crystal X-ray crystallography. The product formation bias resulting from the attack on the zu-face is discussed in terms of transition-state hyperconjugation, but new results for photocycloaddition reactions of 5-trimethylsilyl-substituted adamantan-2-one (1-SiMe 3 ), with both fumaronitrile and methacrylonitrile, show an unprecedented σ-electron-withdrawing characteristic with this substituent.

Original languageEnglish
Pages (from-to)581-586
Number of pages6
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number3
DOIs
StatePublished - 1 Dec 1995

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