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Issue 15, 2018
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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

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Abstract

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.

Graphical abstract: Stabilising fleeting intermediates of stilbene photocyclization with amino-borane functionalisation: the rare isolation of persistent dihydrophenanthrenes and their [1,5] H-shift isomers

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Publication details

The article was received on 02 Feb 2018, accepted on 26 Mar 2018 and first published on 27 Mar 2018


Article type: Edge Article
DOI: 10.1039/C8SC00560E
Citation: Chem. Sci., 2018,9, 3844-3855
  • Open access: Creative Commons BY-NC license
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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

    Y. Shi, S. K. Mellerup, K. Yuan, G. Hu, F. Sauriol, T. Peng, N. Wang, P. Chen and S. Wang, Chem. Sci., 2018, 9, 3844
    DOI: 10.1039/C8SC00560E

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