A series of dibenzo [n.2.2] bicyclic compounds (n = 2-20) were prepared in one step and good yields starting from dimethyl anthracene-9,10-dicarboxylate. Reduction of the aromatic diester using lithium/naphthalene led to a bis-enolate that was cyclized with a variety of bis-electrophiles. The ease of the cyclization is probably due to the puckered conformation of the intermediate formed after the first alkylation step, in which the newly introduced chain that will become the bridge portion occupies a pseudoaxial position, positioning the leaving group close to the enolate nucleophile in the macrocyclization step.

1,2-Aromatic diesters can be transformed into strained bridged polycyclic structures by a two-step procedure consisting of an initial reductive alkylation promoted by alkaline metals, followed by a reaction of the resulting unsaturated diesters with Me3SnLi. We propose that a stanna-Brook rearrangement plays a fundamental role in the formation of the polycyclic organotin acetals obtained. These unusual compounds could be further functionalized by tin–lithium exchange followed by alkylation of the newly formed tertiary carbanion. Alternatively, dialkylated aromatic hydrocarbons have been prepared via a decarbonilation reaction promoted by Me3SnLi. 1,4-Aromatic diesters were reductively dialkylated and then transformed into norbornadienone derivatives by reaction with Me3SnLi. Several stable dibenzonorbornadienones 41 have been prepared in just two steps starting from anthracene 38. The corresponding naphthalene analogues gave 1,4-dialkylnaphthalenes. The synthetic protocols described provide access to structures that are not easily obtained through existing synthetic methodologies.

Bis-enolates with extended π-conjugation, prepared by alkali metal-mediated reduction of several aromatic and unsaturated diesters, can be efficiently and regioselectively alkylated with very hindered C-electrophiles, such as neopentyl, secondary and tertiary alkyl halides, and tosylates. A one-step synthesis of 4-alkyl phthalates was derived from the reductive alkylation of a phthalate diester with hindered halides followed by rearomatization with oxygen. Additionally, synthetic protocols have been developed to efficiently prepare complex fused-or spiro-bicycles from diisopropyl phthalate in just one or two steps.