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Stabilising fleeting intermediates of stilbene photocyclization with amino-borane functionalisation: the rare isolation of persistent dihydrophenanthrenes and their [1,5] H-shift isomers†
Chemical Science ( IF 7.6 ) Pub Date : 2018-03-27 00:00:00 , DOI: 10.1039/c8sc00560e
Yong-gang Shi 1, 2, 3, 4, 5 , Soren K. Mellerup 6, 7, 8, 9 , Kang Yuan 6, 7, 8, 9 , Guo-Fei Hu 1, 2, 3, 4, 5 , Francoise Sauriol 6, 7, 8, 9 , Tai Peng 1, 2, 3, 4, 5 , Nan Wang 1, 2, 3, 4, 5 , Pangkuan Chen 1, 2, 3, 4, 5 , Suning Wang 1, 2, 3, 4, 5
Affiliation  

The key intermediate, 4a,4b-dihydrophenanthrene (DPH), involved in the photocyclization of stilbene and derivatives is known to be unstable, and is therefore poorly characterized/understood. We have found that functionalising stilbenes with NMe2 and BMes2 groups can greatly enhance the stability of 4a,4b-DPHs, allowing quantitative isolation and full characterization of these rare species. Furthermore, we discovered that the new amino-borane decorated 4a,4b-DPHs can undergo thermal [1,5] H sigmatropic shift, forming isomers 4a,10a-DPHs. Both 4a,4b-DHPs and 4a,10a-DHPs are stable towards air and moisture, while only the former were found to undergo oxidative dehydrogenation upon irradiation at 365 nm under air, yielding brightly blue/green fluorescent NMe2 and BMes2 functionalised phenanthrene analogues. Control studies established that the trans-Mes2B–Ph–NMe2 unit is responsible for the stability of these isolated 4a,4b-DHPs and their [1,5]-H shift isomers.

中文翻译:

通过氨基硼烷官能化稳定二苯乙烯ene光环化的短暂中间体:持久性二氢菲及其[1,5] H位移异构体的稀有分离

已知参与二苯乙烯和衍生物光环化的关键中间体4a,4b-二氢菲(DPH)是不稳定的,因此表征/理解较差。我们发现,使用NMe 2和BMes 2基团官能化的斯蒂苯类化合物可以大大增强4a,4b-DPHs的稳定性,从而可以对这些稀有物种进行定量分离和全面表征。此外,我们发现新的氨基硼烷修饰的4a,4b-DPHs可以经历热[1,5] H的σ位移,形成异构体4a,10a-DPHs。4a,4b-DHP和4a,10a-DHP均对空气和湿气稳定,而只有前者在空气中365 nm照射后会发生氧化脱氢,产生明亮的蓝色/绿色荧光NMe 2和BMes 2功能化的菲类似物。对照研究确定,-Mes 2 B–Ph–NMe 2单元负责这些分离的4a,4b-DHP及其[1,5] -H转移异构体的稳定性。
更新日期:2018-03-27
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