Regioselective addition of n-alkyllithium to α,α'-disubstituted-1,8-naphthyridines: Effect of solvent polarity and chelation

ORGN 521

Tae-gyu Nam, tae-gyu.nam@vanderbilt.edu, Maikel Wijtmans, maikel.wijtmans@vanderbilt.edu, and Ned A. Porter. Department of Chemistry, Vanderbilt University, Station B, 351822, Nashville, TN 37235
1,8-naphthyridines provide an important scaffold for a variety of compounds of unique biological activities. Our recent findings demonstrated that they also serve as a key structure for highly efficient chain breaking antioxidant (30 times stronger than α-tocopherol, nature's the most powerful antioxidant). As a methodology for the preparation of gem-dialkyl 1,8-naphthyridine, the addition of n-alkyllithiums to α,α'-disubstituted-1,8-naphthyridines was investigated. High yields were obtained only in non-polar solvents such as ether/hexanes mixture. In more polar solvents, such as THF, alkyllithium acts as a base rather than a nucleophile. Regioselective addition of n-alkyllithiums to α,α'-disubstituted-1,8-naphthyridines was achieved through a cyclic chelation with co-chelating group. Five-membered chelation by TBS protected alcohol moiety turned out to be the most successful. In contrast, six-membered chelation gave marginal regioselectivity. This methodology was successfully incorporated to the synthesis of nitrogen analogs of PMC, an α-tocopherol derivative with 2,2-dimethyl substituents.