Ligand-Controlled Nickel-Catalyzed Reactions of Benzocyclobutenones with Alkynyltrifluoroborates: Diverse Construction of Polysubstituted Naphthols

Ligand-controlled nickel-catalyzed selective cleavage of the C1-C2 or C1-C8 bond of benzocyclobutenones (BCBs) is reported. The delicate selection of dpppe or PMe3 as the ligand led to predictably divergent synthesis of a wide range of 1-naphthols and 2-naphthols without C2 and C3 substituents, respectively, from BCBs and potassium alkynyltrifluoroborate, and the increase in the amount of PMe3 resulted in tandem reaction of 2 equiv of BCB with the borate to afford 3,4,5-trisubstituted 2-naphthols. The fabulous ligand effect resulted in the facile and unique construction of multisubstituted naphthols with well-controlled regioselectivity and a high degree of structural diversity.

Automated summary

Ligand-controlled nickel-catalyzed selective cleavage of the C1-C2 or C1-C8 bond of benzocyclobutenones (BCBs) is reported. The delicate selection of dpppe or PMe3 as the ligand led to the predictable synthesis of a wide range of 1-naphthols and 2-naphthols without C2 and C3 substituents, respectively, from BCBs and potassium alkynyltrifluoroborate, and the increase in the amount of PMe3 resulted in tandem reaction of 2 equiv of BCB with the borate to afford 3,4,5-trisubstituted 2-naphthols. The fabulous ligand effect resulted in the facile and unique construction of multisubstituted naphthols with well-controlled regioselectivity and a high degree of structural diversity.