Palladium catalyzed carbon-carbon bond formation under reductive, oxidative and redox neutral conditions

PhD ceremony: Mr. A.L.N.R. Gottumukkala, 12.45 uur, Academiegebouw, Broerstraat 5, Groningen

Dissertation: Palladium catalyzed carbon-carbon bond formation under reductive, oxidative and redox neutral conditions

Promotor(s): prof. A.J. Meinaard, prof. J.G. de Vries

Faculty: Mathematics and Natural Sciences

Organic chemistry concerns itself with reactions and properties of carbon-based compounds. It is responsible for many of the miracles of chemistry that we experience in our daily life like pharmaceuticals, plastics etc. Central to the study of organic chemistry, are reactions that allow the formation of carbon-carbon bonds. In recent years, the metal palladium has emerged as an excellent catalyst for the formation of these carbon-carbon bonds.

This thesis is dedicated to the study of two such reactions, the Heck reaction and conjugate addition. The Heck reaction was recognized with a Nobel Prize in 2010. This thesis explores each of these reactions under different conditions and the relationship between them. This knowledge allows us to replace several industrially significant reactions that take place with along with the production of large quantities of metal containing waste, with cleaner and cheaper alternatives. Further, studies in this thesis are directed towards the formation of “benzylic quaternary stereocenters” via Pd-catalyzed conjugate addition reaction, a previously unknown application of this reaction. Important attributes of this reaction were discovered. Several challenges were identified, along with their solutions. The advantage of such a reaction is that it replaces reactions that require drastic conditions (controlled reaction-atmosphere, and very low temperatures) or those that require a very precious metal, rhodium. An application of the new development was demonstrated with the synthesis of a natural product, (–) -alpha - cuparenone in only 2 steps, a molecule that previously required anything between 5 and 17 steps.