Kikugawa Yasuo, Nagashima Akira, Sakamoto Takeshi, Miyazawa Etsuko, Shiiya Megumi
Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan.
J Org Chem. 2003 Aug 22;68(17):6739-44. doi: 10.1021/jo0347009.
N-Phthalimido-N-acylnitrenium ions are generated from N-acylaminophthalimides, a new class of precursors, by treatment with hypervalent iodine compounds (PIFA and HTIB). In HFIP, the nitrenium ions undergo intramolecular electrophilic substitution reactions to afford N-aminonitrogen heterocycles in high yields. In TFEA, spirodienones bearing the 1-azaspiro[4.5]decane skeleton are obtained by treatment of N-phthalimido-3-(4-halogenophenyl)propanamides with HTIB as a result of ipso attack of the intermediate nitrenium ion. Similarly, using PIFA in TFEA, ipso cyclization of unactivated benzenoid compounds occurs to afford spirodiene derivatives. This involves loss of aromaticity despite the absence of other activating substituents on the phenyl group.
N-邻苯二甲酰亚氨基-N-酰基氮鎓离子由一类新型前体N-酰基氨基邻苯二甲酰亚胺通过与高价碘化合物（PIFA和HTIB）反应生成。在HFIP中，氮鎓离子发生分子内亲电取代反应，以高产率得到N-氨基氮杂环。在TFEA中，通过用HTIB处理N-邻苯二甲酰亚氨基-3-(4-卤代苯基)丙酰胺，由于中间氮鎓离子的本位进攻，得到具有1-氮杂螺[4.5]癸烷骨架的螺二烯酮。同样，在TFEA中使用PIFA，未活化的苯类化合物发生本位环化反应，得到螺二烯衍生物。尽管苯基上没有其他活化取代基，但这一过程涉及芳香性的丧失。
