Regio-defined multi-hydroxylation of Dibenzo[g,p]chrysene

[Display omitted] •Direct and selective four-fold bromination reactions of dibenzo[g,p]chrysene is demonstrated.•Syntheses of four- and octa-hydroxyl dibenzo[g,p]chrysene as single isomers are achieved.•The torsion angle of the non-planar pi-conjugation reached the largest 41.1° among the angles reported so far. Regioselective direct tetra-bromination of dibenzo[g,p]chrysene (DBC) is described, involving the synthesis of multi-hydroxyl DBC derivatives. Addition of 16 equiv Br2 to a suspension of DBC in CH2Cl2 enables to singly construct a 2,7,10,15-tetrabromo-DBC. A lithium-bromine exchange event leads the corresponding silyl molecule, and the following oxidation formed a tetra-hydroxyl derivative. Its isomeric tetra-hydroxyl DBC as well as more congested octa-hydroxyl DBC were also singly constructed. These straightforward and simple synthetic routes would provide a general entry for new DBC materials.