Department of Chemistry and Biochemistry, University of Denver , Denver, Colorado 80208, United States.
Org Lett. 2015 Feb 6;17(3):438-41. doi: 10.1021/ol5033909. Epub 2015 Jan 14.
Photogenerated azaxylylenes undergo intramolecular cycloadditions to 1,3,4-oxadiazole pendants, which are accompanied by concomitant release of dinitrogen, yielding functionalized ketopiperazinoquinolinols containing an oxirane moiety fused to the quinolinole moiety while spiro-connected to diketopiperazine. These primary photoproducts are reactive versatile intermediates which can be further derivatized under nucleophilic SN1- or SN2-like ring opening of the oxirane moiety. The oxidized quinolinones undergo new rearrangements under the conditions of the Schmidt reaction, leading to unprecedented triazacanoindolinones.
光致氮宾与 1,3,4-噁二唑侧链发生分子内环加成反应，同时伴随着双氮的释放，生成功能化的酮哌嗪并喹啉醇，其中氧杂环丁烷部分与二酮哌嗪稠合，并连接到喹啉醇部分。这些初级光产物是反应性的多功能中间体，可以进一步衍生，通过 SN1 或 SN2 类似的环氧化合物开环反应进行亲核取代。氧化的喹啉酮在 Schmidt 反应条件下发生新的重排，生成前所未有的三氮唑并[1,5-a]吲哚啉酮。
