Zhang Dong, Gao Ruomei, Afzal Shabana, Vargas Mario, Sharma Shantanu, McCurdy Alison, Yousufuddin Muhammed, Stewart Timothy, Bau Robert, Selke Matthias
Department of Chemistry and Biochemistry, California State University-Los Angeles, Los Angeles, CA 90032, USA.
Org Lett. 2006 Oct 26;8(22):5125-8. doi: 10.1021/ol0622007.
Singlet oxygen reacts with binaphthyl phosphine derivatives such as 1,1'-binaphthyl di-tert-butyl phosphine to form the corresponding binaphthyl-2-oxide phosphine oxides. This new intramolecular arene epoxidation reaction proceeds with complete retention of stereochemistry. The binaphthyl-2-oxide di-tert-butyl phosphine oxide undergoes a slow "NIH-rearrangement" to form the corresponding hydroxylated product. A transient phosphadioxirane intermediate has been directly observed by low-temperature NMR. Kinetic analyses show that all of the phosphadioxirane intermediate is converted to product. [reaction: see text]
单线态氧与联萘基膦衍生物（如1,1'-联萘二 - 叔丁基膦）反应，形成相应的联萘 - 2 - 氧化物膦氧化物。这种新的分子内芳烃环氧化反应在立体化学上完全保持不变。联萘 - 2 - 氧化物二叔丁基膦氧化物经历缓慢的“NIH重排”，形成相应的羟基化产物。通过低温核磁共振直接观察到了瞬态磷杂二氧杂环丙烷中间体。动力学分析表明，所有的磷杂二氧杂环丙烷中间体都转化为产物。[反应：见正文]
