Tamura Osamu, Mitsuya Takahiro, Huang Xin, Tsutsumi Yoshiyuki, Hattori Sanae, Ishibashi Hiroyuki
Showa Pharmaceutical University, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan.
J Org Chem. 2005 Dec 23;70(26):10720-5. doi: 10.1021/jo051652e.
[reaction: see text] Intramolecular cycloaddition of novel 1,3-dipoles, N-boranonitrones, was examined. Treatment of O-tert-butyldimethylsilyloximes 9-12 having olefin moieties with 2 equiv of BF3 x OEt2 generated N-boranonitrones, which underwent intramolecular cycloaddition to afford N-nonsubstituted cycloadducts 16 (and/or 18) after extractive workup. Despite the Lewis-acidic conditions, the olefin geometry of the substrates was retained in the cycloadducts in the present cycloaddition. The electronic nature of the N-boranonitrones appeared to be electrophilic. In the case of substrate 11c, having an electron-donating methyl group at an internal position of the olefin moiety, the cycloaddition gave the bridged cycloadduct 18b. The cycloaddition proceeded at relatively low temperature, and the diastereoselectivity was high.
