Davies Ian W, Guner Vildan A, Houk K N
Department of Process Research, Merck & Co. Inc., Rahway, NJ 07065-0900, USA.
Org Lett. 2004 Mar 4;6(5):743-6. doi: 10.1021/ol0364273.
Deoxygenation of nitroaromatics is a classic synthetic method for the construction of nitrogen heterocycles. The generally accepted mechanism involves exhaustive deoxygenation to a singlet nitrene. We present theoretical evidence for an alternative, 6pi-electron 5-atom electrocyclization of nitroso-styrenes, -stilbenes, and -biphenyls to nitronates. A downstream 1,5-H shift and tautomerization leads to N-hydroxy heterocycles. [reaction: see text]
硝基芳烃的脱氧反应是构建氮杂环的经典合成方法。普遍接受的机理涉及将其彻底脱氧为单线态氮烯。我们提供了理论证据，证明亚硝基苯乙烯、亚硝基芪和亚硝基联苯可通过另一种6π电子5原子电环化反应生成硝酮。下游的1,5-氢迁移和互变异构会生成N-羟基杂环。[反应：见正文]
