APPLICATION OF Pd(OCOCF[3]) [2]/BIPYRIDINE COMPLEX IN THE FORMATION OF QUATERNARY CARBON CENTERS


                                          Jasmin Suljagić


         Faculty of Technology, Urfeta Vejzagića br.8, 75000 Tuzla, Bosnia and Herzegovina
                                      jasmin.suljagic@untz.ba

                                             Abstract

The benzylic quaternary center is a widely prevalent motif in a multitude of biologically active
natural products, drug candidates, and fragrances. The challenge of installing these centers in a
straightforward and selective manner continues to receive much attention in recent literature.
Transition-metal catalysis offers a spectrum of reactions to address this challenge. In this
respect, few reactions have enjoyed the success, tenability, and reliability of conjugate addition
reactions to ß,ß-disubstituted enones. An efficient protocol for the formation of benzylic
quaternary centers via arylation of enones using a catalyst made from Pd(O[2]CCF[3])[2] and
2,2′-bipyridine is developed. For cyclic substrates, catalyst loadings as low as 1 mol % Pd are
enough to afford excellent yields (>90 %) using a variety of arylboronic acids. In the case of
acyclic substrates, the addition of KSbF[6] was found to improve conversions and yields.

Keywords: arylations, C - C coupling reactions, enones, ligands, palladium


Literature:


1.        J. A. Jordan-Hore, J. N. Sanderson, A.-L. Lee, Org. Lett. 2012, 14, 2508.

2.        A. L. Gottumukkala, K. Matcha, M. Lutz, J. G. de Vries, A. J. Minnaard, Chem. Eur. J.
2012, 18, 6907.

3.        R. Shintani, M. Takeda, T. Nishimura, T. Hayashi, Angew. Chem. 2010, 122, 4061; Angew.
Chem. Int. Ed. 2010, 49, 3969.