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Osmium(II) CNN pincer complexes as efficient catalysts for both asymmetric transfer and H2 Hydrogenation of Ketones

Baratta, Walter and Ballico, Maurizio and Chelucci, Giorgio Adolfo and Siega, Katia and Rigo, Pierluigi (2008) Osmium(II) CNN pincer complexes as efficient catalysts for both asymmetric transfer and H2 Hydrogenation of Ketones. Angewandte Chemie. International Edition, Vol. 47 (23), p. 4362-4365. eISSN 1521-3773. Article.

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DOI: 10.1002/anie.200800339

Abstract

We describe the isolation of the first CNN pincer osmium complexes [OsX(CNN)P2] to display high catalytic activity and productivity in the reduction of ketones by either TH or HY (TOFand TON up to 106 h1 and 105, respectively). A high enantioselectivity (up to 98% ee) is possible in both reactions with a remarkably low catalyst loading (0.005–0.002 mol%). To the best of our knowledge, this is the first example of an osmium complex that catalyzes the asymmetric HY of ketones. Evidence for an Os-OR vs. Os-H equilibrium suggests that both these species are involved in the catalytic pathways. Mechanistic studies as well as the preparation of new CNN pincer osmium catalysts are currently underway.

Item Type:Article
ID Code:1839
Status:Published
Refereed:Yes
Uncontrolled Keywords:Asymmetric catalysis, hydrides, hydrogen transfer, hydrogenation, osmium
Subjects:Area 03 - Scienze chimiche > CHIM/06 Chimica organica
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Wiley
eISSN:1521-3773
Deposited On:18 Aug 2009 10:06

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