Cu super(II)-Catalyzed Asymmetric Hydrosilylation of Diaryl- and Aryl Heteroaryl Ketones: Application in the Enantioselective Synthesis of Orphenadrine and Neobenodine

With certain amounts of sodium tert-butoxide and tert-butanol as additives, catalytic amounts of an inexpensive and easy-to-handle copper source Cu(OAc) sub(2)H sub(2)O, a commercially available and air-stable non-racemic dipyridylphosphine ligand, as well as the stoichiometric desirable hydride don...

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Bibliographic Details
Published in:Chemistry : a European journal 2012-06, Vol.18 (24), p.7486-7492
Main Authors: Sui, Yao-Zong, Zhang, Xi-Chang, Wu, Jun-Wen, Li, Shijun, Zhou, Ji-Ning, Li, Min, Fang, Wenjun, Chan, Albert SC, Wu, Jing
Format: Article
Language:English
Subjects:
Aromatic compounds
Asymmetry
Catalysts
Copper
Hydrosilylation
Ketones
Sodium
Synthesis
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Summary:With certain amounts of sodium tert-butoxide and tert-butanol as additives, catalytic amounts of an inexpensive and easy-to-handle copper source Cu(OAc) sub(2)H sub(2)O, a commercially available and air-stable non-racemic dipyridylphosphine ligand, as well as the stoichiometric desirable hydride donor polymethylhydrosiloxane (PMHS), formed a versatile in situ catalyst system for the enantioselective reduction of a broad spectrum of prochiral diaryl and aryl heteroarylketones in air, in high yields and with good to excellent enantioselectivities (up to 96%). In particular, the practical viability of this process was evinced by its successful applications in the asymmetric synthesis of optically enriched potent antihistaminic drugs orphenadrine and neobenodine. Could do with a copper: The Cu-catalyzed conversion of diaryl- and aryl heteroaryl ketones into their corresponding alcohols proceeded in high yields and with good to excellent ee values. This process was used in the asymmetric synthesis of two anti histamines.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201200379