Asymmetric hydrogenation of alkynyl ketones with the η(6)-arene/TsDPEN-ruthenium(II) catalyst

Enantioselective hydrogenation of alkynyl ketones catalyzed by Ru(OTf)(TsDPEN)(η(6)-p-cymene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) affords the propargylic alcohols in up to 97% ee. The alkynyl moieties are left intact in most cases. The reaction can be conducted with a substr...

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Bibliographic Details
Published in:Organic letters 2013-06, Vol.15 (12), p.3030-3033
Main Authors: Arai, Noriyoshi, Satoh, Hironori, Utsumi, Noriyuki, Murata, Kunihiko, Tsutsumi, Kunihiko, Ohkuma, Takeshi
Format: Article
Language:English
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Summary:Enantioselective hydrogenation of alkynyl ketones catalyzed by Ru(OTf)(TsDPEN)(η(6)-p-cymene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) affords the propargylic alcohols in up to 97% ee. The alkynyl moieties are left intact in most cases. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 5000 under 10 atm of H2. The mode of enantioselection is elucidated with the transition state models directed by the CH/π attractive interaction between the substrate and the catalytic species.
ISSN:1523-7052
DOI:10.1021/ol4012184