A Co(0)-catalyzed intramolecular alkyne/benzocyclobutenone coupling through C-C cleavage of benzocyclobutenones is described. Co2(CO)8/P[3, 5-(CF3)2C6H3]3 was discovered to be an effective metal/ligand combination, which exhibits complementary catalytic activity to the previously established rhodium catalyst. In particular, the C8-substituted substrates failed in the Rh system, but succeeded with the Co catalysis. Experimental and computational studies show that the initially formed tetrahedral dicobalt-alkyne complex undergoes C1-C2 activation via oxidative addition with Co(0), followed by migratory insertion and reductive elimination to give the β-naphthol products.
A Co(0)-catalyzed intramolecular pan class="Chemical">alkyne/benzocyclobutenonecoupling through C-C cleavage of benzocyclobutenones is described. Co2(CO)8/P[3, 5-(CF3)2C6H3]3 was discovered to be an effective metal/ligand combination, which exhibits complementary catalytic activity to the previously established rhodium catalyst. In particular, the C8-substituted substrates failed in the Rh system, but succeeded with the Co catalysis. Experimental and computational studies show that the initially formed tetrahedral dicobalt-alkynecomplex undergoes C1-C2 activation via oxidative addition with Co(0), followed by migratory insertion and reductive elimination to give the β-naphthol products.
Authors: Korkit Korvorapun; Marc Moselage; Julia Struwe; Torben Rogge; Antonis M Messinis; Lutz Ackermann Journal: Angew Chem Int Ed Engl Date: 2020-08-25 Impact factor: 16.823