Rapid Access to Orthogonally Functionalized Naphthalenes: Application to the Total Synthesis of the Anticancer Agent Chartarin.

We report the synthesis of orthogonally functionalized naphthalenes from simple, commercially available indanones in four steps. The developed method proceeds through a two-step process that features a thermally induced fragmentation of a cyclopropane indanone with simultaneous 1,2-chloride shift. Migration of the chloride substituent occurs in a regioselective manner to preferentially afford the para-chloronaphthol substitution pattern.

A transition-metal-free synthesis of fluorinated naphthols.

Herein, we describe a transition-metal-free protocol for the conversion of simple 2-allyl-3-(trifluoromethyl)phenols into substituted 5-fluoronaphthalen-1-ols. The key events of this reaction include the selective activation of two C-F bonds and formation of an intermediate hexatriene system, which undergoes a 6π electrocyclization, followed by rearomatization. This concept enables the rapid conversion (three steps) of various commercially available 3-(trifluoromethyl)phenols into novel fluorine-containing naphthols, which are difficult to prepare by previous methods.

Annelated pyridines as highly nucleophilic and Lewis basic catalysts for acylation reactions.

New heterocyclic derivatives of 9-azajulolidine have been synthesized and characterized with respect to their nucleophilicity and Lewis basicity. The Lewis basicity of these bases as quantified through their theoretically calculated methyl-cation affinities correlate well with the experimentally measured reaction rates for addition to benzhydryl cations. All newly synthesized pyridines show exceptional catalytic activities in benchmark acylation reactions, which correlate only poorly with Lewis basicity or nucleophilicity parameters.