Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt , Max-von-Laue-Strasse 7 , D-60438 Frankfurt (Main) , Germany.
Department of Chemistry , Queen's University , Kingston , Ontario K7L 3N6 , Canada.
Org Lett. 2018 Jul 6;20(13):3966-3970. doi: 10.1021/acs.orglett.8b01534. Epub 2018 Jun 14.
The photoreactivity of 9-borafluorene-based, C,C-chelated organoborates was investigated. Unlike the related tetraarylborates, the charge-transfer transitions imparted by the biphenyl chelate lead to selective insertion of one aryl substituent into the endocyclic B-C bond of the 9-borafluorene moiety, resulting in the formation of boratanorcaradienes. This photoreaction likely proceeds according to a Zimmerman rearrangement, which is analogous to one of the initially proposed mechanisms for tetraarylborates and provides additional insight into these long-debated photochemical reactions.
研究了基于 9-硼芴的、C,C-螯合的有机硼酸酯的光反应性。与相关的四芳基硼酸酯不同，由联苯螯合赋予的电荷转移跃迁导致一个芳基取代基选择性地插入 9-硼芴部分的内环 B-C 键中，从而形成硼杂萘并二烯。这种光反应可能按照 Zimmerman 重排进行，类似于最初提出的四芳基硼酸酯的机制之一，为这些长期争论的光化学反应提供了更多的见解。
