Cu Catalyzed Cross Coupling Darien Yeung 1

Cu Catalyzed Cross Coupling Darien Yeung 1

Roadmap 1) Cross-Coupling Relevance since establishment of technique 2) Examples of Cu Catalyzed Cross Coupling 3) Mechanism of Catalysis Relevance Examples of Cu Cross Coupling Mechanism 2

How did it all start? Johansson Seechurn et al., Angew. Chem. Int. Ed., 2012 Relevance Examples of Cu Cross Coupling Mechanism 3

Ullman Reaction Relevance Examples of Cu Cross Coupling Mechanism 4

Ullmann Reaction CuI 20min @ 220oC I 2 Relevance Examples of Cu Cross Coupling Mechanism 5

Ullmann Catalytic Cycle Ar-Nu HNu Base CuI Base HI Reductive Elimination Ar I Cu Cu-Nu Nu Relevance Oxidative Addition Examples of Cu Cross Coupling ArI Mechanism 6

Stephens-Castro Reaction I Cu R MeO Pyridine, N2 10hrs @ 120oC Relevance MeO Examples of Cu Cross Coupling R Mechanism 7

How does the Reaction Work? ie. Nuc OMe Go, J., Liu, P., Houk, KN., Buchwald, SL., J. Am. Chem. Soc., 2010 Relevance Examples of Cu Cross Coupling Mechanism 8

Case 1) Electron Donating Ligand O I (EDG)CuI O O ie. EDG Me I Single Electron Transfer (EDG)CuII O (EDG)CuII O (EDG)CuII O Relevance Examples of Cu Cross Coupling I I Mechanism 9

Case II) Electron Withdrawing Ligand I (EWG)Cu I ie. EWG O N N I Iodine Atom Transfer (EWG) CuII O I (EWG) CuII O Relevance Examples of Cu Cross Coupling Mechanism 10

Questions? 11