10.1021/acs.joc.5b00931.s006 Paul F. Thomson Paul F. Thomson Damon Parrish Damon Parrish Padmanava Pradhan Padmanava Pradhan Mahesh K. Lakshman Mahesh K. Lakshman Modular, Metal-Catalyzed Cycloisomerization Approach to Angularly Fused Polycyclic Aromatic Hydrocarbons and Their Oxidized Derivatives American Chemical Society 2015 benzo THF PtCl 2 BBr 3 NaBH 4 Angularly Fused Polycyclic Aromatic Hydrocarbons series 1 diol epoxides 2O HO oxygen atmosphere acid hydrocarbon DDQ ethynylphenyl isomeric series 2 diol epoxides Cycloisomerization IRA PDC BcPh derivatives dihydrodiol 2015-08-07 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Modular_Metal_Catalyzed_Cycloisomerization_Approach_to_Angularly_Fused_Polycyclic_Aromatic_Hydrocarbons_and_Their_Oxidized_Derivatives/2142778 Palladium-catalyzed cross-coupling reactions of 2-bromobenzaldehyde and 6-bromo-2,3-dimethoxybenzaldehyde with 4-methyl-1-naphthaleneboronic acid and acenaphthene-5-boronic acid gave corresponding <i>o</i>-naphthyl benzaldehydes. Corey–Fuchs olefination followed by reaction with <i>n</i>-BuLi led to various 1-(2-ethynylphenyl)­naphthalenes. Cycloisomerization of individual 1-(2-ethynylphenyl)­naphthalenes to various benzo­[<i>c</i>]­phenanthrene (B<i>c</i>Ph) analogues was accomplished smoothly with catalytic PtCl<sub>2</sub> in PhMe. In the case of 4,5-dihydrobenzo­[<i>l</i>]­acephenanthrylene, oxidation with DDQ gave benzo­[<i>l</i>]­acephenanthrylene. The dimethoxy-substituted benzo­[<i>c</i>]­phenanthrenes were demethylated with BBr<sub>3</sub> and oxidized to the <i>o</i>-quinones with PDC. Reduction of these quinones with NaBH<sub>4</sub> in THF/EtOH in an oxygen atmosphere gave the respective dihydrodiols. Exposure of the dihydrodiols to <i>N</i>-bromoacetamide in THF-H<sub>2</sub>O led to bromohydrins that were cyclized with Amberlite IRA 400 HO<sup>–</sup> to yield the series 1 diol epoxides. Epoxidation of the dihydrodiols with <i>m</i>CPBA gave the isomeric series 2 diol epoxides. All of the hydrocarbons as well as the methoxy-substituted ones were crystallized and analyzed by X-ray crystallography, and these data are compared to other previously studied B<i>c</i>Ph derivatives. The methodology described is highly modular and can be utilized for the synthesis of a wide variety of angularly fused polycyclic aromatic hydrocarbons and their putative metabolites and/or other derivatives.