Synthesis, reduction and C-H activation chemistry of azaborinines with redox-active organoboryl substituents

The 2,3,4,5,6-pentaphenyl-1,2-azaborinin-1-yl (PPAB) potassium complex 1 undergoes facile salt metathesis with 9,10-dibromo-9,10-dihydroboraanthracene (DBABr2), 5-bromodibenzo[b,d]borole (DBBBr), 1-chlorotetraphenylborole (TPBCl) and dibromo(phenyl)borane (BBr2Ph) to yield the corresponding N-borylated azaborinines N-DBABr-PPAB (2, which hydrolyses and dimerises to the oxo-bridged N,N '-O(DBA)2-(PPAB)2, 3), N,N '-DBA-(PPAB)2 (4), N-DBB-PPAB (5), N-PPB-PPAB (7) and N-BBrPh-PPBA (9). Stepwise reduction of 4 yields the corresponding stable radical anion 4- and dianion 42-. One-electron reduction of 5 with KC8 yields the purple radical anion 5-, which forms a highly insoluble coordination polymer. 5- undergoes very slow radical intramolecular ortho-C-H activation at the C4-phenyl substituent of the PPAB moiety, yielding a BN-analogue of the 5,5 '-spiro-bi[dibenzoborole] anion, [6]K. Compound 7 cannot be isolated and undergoes spontaneous and diastereoselective 2,5-anti-addition of the ortho-C-H bond of the PPAB C4-phenyl substituent to yield a novel BNB-analogue of the triply fused dihydrocyclopenta[l]phenanthrene cation, compound 8. Finally the one-electron reduction of 9 results in the ortho-C-H activation of the PPAB C4-phenyl substituent at an in situ-generated dicoordinate boryl anion (10), resulting in the formation of a BNB-analogue of 9H-fluorene, the borate 11-. DFT calculations provide a rationale for the diverse C-H activations observed in these reactions. N-borylation of a 1,2-azaborinine with boron-doped (anti)aromatic substituents provides access to a range of novel BNB-doped multiply fused heterocycles resulting from the spontaneous or reductive intramolecular C-H activation of a phenyl residue.