Enantioselective hydrogenation of olefins with phosphinooxazoline-iridium catalysts

✍ Scribed by Donna G. Blackmond; Andrew Lightfoot; Andreas Pfaltz; Thorsten Rosner; Patrick Schnider; Nicole Zimmermann

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 168 KB
• Volume: 12
• Category: Article
• ISSN: 0899-0042
• DOI: 10.1002/(sici)1520-636x(2000)12:5/6<442::aid-chir25>3.0.co;2-f

✦ Synopsis

Cationic iridium complexes with chiral phosphinooxazoline ligands are efficient catalysts for the enantioselective hydrogenation of olefins. The complexes are readily prepared, air-stable, and easy to handle. In contrast to chiral rhodium- and ruthenium-phosphine catalysts, they do not require the presence of a polar coordinating group near the C=C bond. In the hydrogenation of unfunctionalized trisubstituted 1,2-diaryl-olefins, high enantioselectivities of >95% ee with full conversion and turnover frequencies of >7,000 h-1 can be achieved, using 0.1 mol% of catalyst with tetrakis[3, 5-bis(trifluoromethyl)phenyl]borate (TFPB or BARF) as the counterion. The corresponding hexafluorophosphate or tetrafluoroborate salts give low conversion due to deactivation of the catalyst during the reaction. Substrates with polar substituents such as allylic alcohols, on the other hand, afford better results with the hexafluorophosphate salts.