Ru(II)-Catalyzed [4 + 2]-Annulation and Arylation of 1,4-Naphthoquinones.

Naphthoquinones form the core of a variety of drugs and natural products. As a result, the conjugation of 1,4-naphthoquinones with organic building blocks would offer a facile strategy toward scaffolds of biological interest. In this regard, we hereby report a Ru(II)-catalyzed [4 + 2] annulation of 1,4-naphthoquinones with benzoic acids to afford various naphthoquinone lactones. Additionally, ketone directed arylation of naphthoquinones using acetophenones under Ru(II)-catalysis was also illustrated. The feedstock availability of these precursors allowed access to a large library of naphthoquinone derivatives in good to excellent yields under fairly mild conditions. The practicality of these protocols was justified by carrying out a gram scale synthesis and further functionalizations. Also, preliminary mechanistic studies were carried out to probe the reaction mechanism.