Osmium(0)-Catalyzed C–C Coupling of Ethylene and α-Olefins with Diols, Ketols, or Hydroxy Esters via Transfer Hydrogenation

In connection with the development of C-C bond forming hydrogenations and transfer hydrogenations beyond hydroformylation,8 we recently found that zerovalent ruthenium complexes generated in situ from Ru3(CO)12 and various phosphine ligands catalyze the CC coupling of vicinally dioxygenated hydrocarbons with diverse π-unsaturated reactants, including dienes,9a–d acrylates9e and alkynes.9g,h,j As in related ruthenium(0) catalyzed Pauson-Khand reactions of vicinal dicarbonyl compounds described by Chatani and Murai,10 these processes are initiated through C=C/C=O oxidative coupling to furnish oxaruthenacycles

Boyoung Y. Park

2016

Scholarcy highlights

  • Introduction α-Olefins are the most abundant petrochemical feedstock beyond alkanes. Despite their ubiquity and low cost, the use of α-olefins in the commercial manufacture of commodity chemicals is largely restricted to polymerization, hydroformylation and alkene metathesis
  • In connection with the development of C-C bond forming hydrogenations and transfer hydrogenations beyond hydroformylation, we recently found that zerovalent ruthenium complexes generated in situ from Ru3(CO) and various phosphine ligands catalyze the CC coupling of vicinally dioxygenated hydrocarbons with diverse π-unsaturated reactants, including dienes,9a–d acrylates9e and alkynes.9g,h,j As in related ruthenium(0) catalyzed Pauson-Khand reactions of vicinal dicarbonyl compounds described by Chatani and Murai, these processes are initiated through C=C/C=O oxidative coupling to furnish oxaruthenacycles
  • In continuing efforts to broaden the scope of transfer hydrogenative α-olefin coupling, we demonstrate that osmium(0) catalysts overcome this limitation, enabling the direct C-C coupling of ethylene and higher α-olefins with diverse diols, α-ketols and α-hydroxy esters
  • We have shown that osmium(0) complexes derived from Os3(CO) and XPhos catalyze the transfer hydrogenative C-C coupling of ethylene and higher α-olefins with diverse vicinally dioxygenated hydrocarbons
  • A challenge associated with the design of transfer hydrogenative coupling of α-olefins with simple primary alcohols will reside in the identification of metal catalysts that are sufficiently electron rich so as to promote oxidative coupling, and whose low-valent forms are accessible through alcohol mediated reduction of the high-valent ions
  • Intermolecular catalytic reductive couplings of α-olefins with unactivated carbonyl compounds remain an unmet challenge in chemical research.22

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