Institut de Chimie Moléculaire et des Matériaux d'Orsay, Université de Paris-Sud, Orsay, France.
Chemistry. 2013 Apr 26;19(18):5557-60. doi: 10.1002/chem.201300195. Epub 2013 Mar 18.
Spirocyclic structures: Nitroso-Diels-Alder reactions of 1,3-disubstituted cyclohexadienes were found to be regiodivergent, depending on the nitroso derivative used. Cycloaddition with Wightman's chloronitroso derivative was totally regio- and stereoselective. This methodology was applied to the synthesis of heterospiranic frameworks after N-O bond cleavage and cyclization (see scheme; Boc=tert-butoxycarbonyl, Tf=trifluoromethanesulfonyl).
发现 1,3-二取代环己二烯的亚硝基-Diels-Alder 反应具有区域选择性，具体取决于所使用的亚硝基衍生物。与 Wightman 的氯代亚硝基衍生物的环加成反应具有完全的区域和立体选择性。该方法在 N-O 键断裂和环化后被应用于杂螺环骨架的合成（见方案；Boc=叔丁氧羰基，Tf=三氟甲磺酸基）。
