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Synthesis, bridgehead functionalization, and photoisomerization of 9,10-diboratatriptycene dianions

Prey, Sven E., Gilmer, Jannik, Teichmann, Samira V., Čaić, Luis, Wenisch, Mischa, Bolte, Michael, Virovets, Alexander, Lerner, Hans‐Wolfram, Fantuzzi, Felipe, Wagner, Matthias and others. (2023) Synthesis, bridgehead functionalization, and photoisomerization of 9,10-diboratatriptycene dianions. Chemical Science, 14 (20). pp. 5316-5322. ISSN 2041-6520. E-ISSN 2041-6539. (doi:10.1039/D3SC00555K) (KAR id:100314)

Abstract

9,10-Diboratatriptycene salts M2[RB(μ-C6H4)3BR] (R = H, Me; M+ = Li+, K+, [n-Bu4N]+) have been synthesized via [4+2] cycloaddition between doubly reduced 9,10-dihydro-9,10-diboraanthracenes M2[DBA] and benzyne, generated in situ from C6H5F and C6H5Li or LiN(i-Pr)2. [HB(μ-C6H4)3BH]2– reacts with CH2Cl2 to form quantitatively the bridgehead-derivatized [ClB(μ‑C6H4)3BCl]2–, while twofold H– abstraction with B(C6F5)3 in the presence of SMe2 leads cleanly to the diadduct (Me2S)B(μ‑C6H4)3B(SMe2). Photoisomerization of K2[HB(μ-C6H4)3BH] (THF, medium-pressure Hg lamp) provides facile access to diborabenzo[a]fluoranthenes, a little explored form of boron-doped polycyclic aromatic hydrocarbons. According to DFT calculations, the underlying reaction mechanism consists of three main steps: (i) photoinduced di-π-borate rearrangement, (ii) “walk reaction” of a BH unit, and (iii) boryl anion-like C–H activation.

Item Type: Article
DOI/Identification number: 10.1039/D3SC00555K
Uncontrolled keywords: General Chemistry
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Funders: German Academic Exchange Service (https://ror.org/039djdh30)
University of Kent (https://ror.org/00xkeyj56)
Depositing User: Felipe Fantuzzi
Date Deposited: 03 Mar 2023 16:02 UTC
Last Modified: 04 Mar 2024 17:23 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/100314 (The current URI for this page, for reference purposes)

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