Synthesis and structure of nitrones derived from 2-trifluoromethyl bornane 3-imines

Upon treatment with (trifluoromethyl)trimethylsilane (CF(3)SiMe(3)), 3-(N-alkyl or 3-N-aryl)imines of camphorquinone of type 1 smoothly undergo stereoselective conversion to yield 2-endo-trifluoromethylated 1:1 adducts 2, which, after subsequent desilylation with sodium borohydride in boiling alcoholic solutions, were converted into imino alcohols 3. Unexpectedly, oxidation of 3 with m-CPBA resulted in the formation of a new type of trifluoromethylated nitrones 5 (and not the expected oxaziridines) in a stereoselective manner. In the case of 5a, the (Z)-configuration of the C=N double bond of the nitrone unit was unambiguously established by an X-ray crystal-structure determination. However, photolysis of 5a led to the exo,exo/exo,endo mixture of the isomeric oxaziridine 7: the two stereoisomers were separated chromatographically. (C) 2010 Elsevier B.V. All rights reserved.