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Published on: March 25, 2017
Aryl Insertion vs Aryl-Aryl Coupling in C,C-Chelated Organoborates: The "Missing Link" of Tetraarylborate
Julian Radtke1, Soren K Mellerup2, Michael Bolte1
1Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt , Max-von-Laue-Strasse 7 , D-60438 Frankfurt (Main) , Germany.
Abstract:
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.
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