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Homogeneous Hydrogenation of Tri‐ and Tetrasubstituted Olefins: Comparison of Iridium‐Phospinooxazoline [Ir‐PHOX] Complexes and Crabtree Catalysts with Hexafluorophosphate (PF 6 ) and Tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (BAr F ) as Counterions
Author(s) -
Wüstenberg Bettina,
Pfaltz Andreas
Publication year - 2008
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200700438
Subject(s) - iridium , chemistry , hexafluorophosphate , oxazoline , trifluoromethyl , catalysis , medicinal chemistry , reactivity (psychology) , boron , organometallic chemistry , counterion , ligand (biochemistry) , ionic liquid , organic chemistry , ion , medicine , alkyl , alternative medicine , pathology , biochemistry , receptor
Four iridium complexes with achiral phosphino‐oxazoline (PHOX) ligands were readily prepared in two steps starting from commercially available phenyloxazolines. The air‐stable complexes with tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate (BAr F ) as counterion showed high reactivity in the hydrogenation of a range of tri‐ and tetrasubstituted olefins. The best results were obtained with an iridium complex ( 11 ) derived from a dicyclohexylphosphino‐oxazoline ligand bearing no additional substituents in the oxazoline ring. With several substrates, which gave only low conversion with the Crabtree catalyst, [Ir(Py)(PCy 3 )(COD)]PF 6 , full conversion was observed. The productivity of the Crabtree catalyst could be strongly increased by replacing the hexafluorophosphate anion with tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate. In one case, in the hydrogenation of a tetraalkyl‐substituted CC bond, [Ir(Py)(PCy 3 )(COD)]BAr F gave higher conversion than catalyst 11 . However, with several other substrates complex 11 proved to be superior.