Ruthenium-Catalyzed Transfer Hydrogenation for C–C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs

Diols as Dienophiles: Bridged Carbocycles via Ruthenium(0)‐Catalyzed Transfer Hydrogenative Cycloadditions of Cyclohexadiene or Norbornadiene

“…From this initial ligand screen, it was found that the ruthenium(0) catalyst modified by bis(diphenylphosphino)ethane (dppe) delivered the hydroxy‐substituted bridged bicycle 3 a in 77 % yield with complete levels of exo ‐selectivity. As depicted in Figure , our collective studies on the ruthenium(0)‐catalyzed C−C coupling of alcohols are consistent with catalytic mechanisms involving diene–dione oxidative coupling to form oxaruthenacycles. In certain cases, such oxaruthenacycles are isolable, suggesting they likely represent resting states in the catalytic cycle and potentially contribute to diminished catalytic efficiency.…”

Neutral chiral cyclopentadienyl Ru(ii)Cl catalysts enable enantioselective [2+2]-cycloadditions

“…Homogenous ruthenium complexes constitute a cornerstone of modern transition-metal catalysis. 1 Besides metathesis catalysts 2 and complexes employed for hydrogenations, 3 cyclopentadienyl (Cp) or pentamethylcyclopentadienyl (Cp*) ruthenium( ii ) complexes, in particular CpRu(CH 3 CN) 3 PF 6 and Cp*Ru(COD)Cl (COD = 1,5-cyclooctadiene), are highly valuable catalysts for atom-economic carbon–carbon and carbon-heteroatom bond formations. 4 One reason is their high number of available and freely accessible coordination sites.…”

Catalytic C(sp3)–H bond activation in tertiary alkylamines

“…With an estimated 26% of all drugs and agrochemicals featuring a tertiary alkylamine 1,2 , the development of robust catalytic methods to assemble and modify the structure of these important molecular features provides a continual challenge to chemical synthesis [3][4][5][6][7][8][9][10][11][12] . A selective single-step transformation of a traditionally unreactive C-H bond, proximal to the nitrogen atom, into a versatile chemical entity would be a particularly powerful strategy for introducing functional complexity to tertiary alkylamines.…”