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Asymmetric Diels-Alder reactions of unsaturated beta-ketoesters catalyzed by chiral ruthenium PNNP complexes.

Authors:
Christoph Schotes Antonio Mezzetti

J Am Chem Soc 2010 Mar;132(11):3652-3

Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093 Zürich, Switzerland.

Cyclic alpha-unsaturated beta-ketoesters undergo cycloaddition with di- and trisubstituted butadienes to give tetrahydro-1-indanone derivatives with up to 93% ee in the presence of a ruthenium catalyst formed by activation of [RuCl(2)(PNNP)] with (Et(3)O)PF(6) (2 equiv) (PNNP = (1S,2S)-N,N'-bis[o-(diphenylphosphino)benzylidene]cyclohexane-1,2-diamine). The protocol has been used to prepare the estrone derivative (8R,13S,14S)-13-tert-butoxycarbonyl-3-methoxy-7,8,12,13,15,16-hexahydro-6H-cyclopenta[a]phenanthren-17(14H)-one as a single diastereoisomer with 85% yield and 99% ee after one crystallization step. Its absolute configuration, which has been determined by X-ray diffraction after reduction to the alcohol and esterification with camphanic chloride, is in agreement with the attack of the diene onto the open enantioface of the beta-keto ester (O-O) in the ruthenium complex [Ru(O-O)(PNNP)](2+), whose X-ray structure has been determined.

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http://dx.doi.org/10.1021/ja910039eDOI Listing
March 2010

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