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Application of the BHQ Reaction in Organic Synthesis: A Synthesis of Plumbagin and Related Compounds

Albakri, Mohammad Izharul

[Thesis]. Manchester, UK: The University of Manchester; 2015.

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Abstract

The thesis concerns the development of 5-hydroxy-2-methylnaphthalene-1,4,-dione (plumbagin) synthesis. It is a natural product with antibiotic and anti-cancer activity, and this particular novel synthetic route to plumbagin utilises 1,4-dimethoxy-2-methyl benzene as a starting material. Plumbagin serves to exemplify the application of a new benzannulation reaction (the “BHQ Reaction”) during organic synthesis. The key step in the production process uses copper-catalysed conversion of 2-allyl-3,6-dimethoxy-4-methylphenyl 2',2',2'-tribromoacetate into 5-bromo-1,4-dimethoxy-2-methtylnaphthalene using the BHQ protocol. It is then subsequently converted from 5-bromo-1,4-dimethoxy-2-methtylnaphthalene into 2'-(5,8-dimethoxy-6-methylnaphthalen-1-yl)-4',4',5',5'-tetramethyl-1',3',2'-dioxaborolane which is followed by a mild oxidation to afford 2-methyl-5-(4',4',5',5',-tetramethyl-1',3',2'dioxaboran-2'-yl)-1,4-dione. Chemoselective oxidation of this quinone with m-CPBA affords the compound, plumbagin. The bromide precursor to plumbagin was also coupled to 2'-(5,8-dimethoxy-6-methylnaphthalen-1-yl)-4',4',5',5'-tetramethyl-1',3',2'-dioxaborolane via palladium cross-coupling to give 5,5',8,8'-tetramethoxy-6,6'-dimetheyl-1,1'-binaphthalene, a novel binaphthalene related to plumbagin.