Catalytic Methylation of C?H Bonds Using CO2 and H2

Formation of C C bonds from CO₂ is a much sought after reaction in organic synthesis. To date, other than C H carboxylations using stoichiometric amounts of metals, base, or organometallic reagents, little is known about C C bond formation. In fact, to the best of our knowledge no catalytic methylation of C H bonds using CO₂ and H₂ has been reported. Described herein is the combination of CO₂ and H₂ for efficient methylation of carbon nucleophiles such as indoles, pyrroles, and electron‐rich arenes. Comparison experiments which employ paraformaldehyde show similar reactivity for the CO₂/H₂ system.     

C?NH2 Bond Formation Mediated by Iridium Complexes

In the presence of phosphanes (PR₃), the amido‐bridged trinuclear complex [{Ir(μ‐NH₂)(tfbb)}₃] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2‐η²‐4‐κ‐C₁₂H₈F₄N)(PR₃)₃], which are the products of the C N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e⁻ complex [Ir(Cl)(tfbb)(PMePh₂)₂] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH₂ moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule.