Enantioselective copper-catalysed propargylic substitution: synthetic scope study and application in formal total syntheses of (+)-anisomycin and (-)-cytoxazone

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107

作者：

Dr. Remko J. Detz Zohar Abiri Remi le Griel Prof. Dr. Henk Hiemstra Dr. Jan H. van Maarseveen

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摘要：

A copper catalyst with a chiral pyridine-2,6-bisoxazoline (pybox) ligand was used to convert a variety of propargylic esters with different side chains (R=Ar, Bn, alkyl) into their amine counterparts in very high yields and with good enantioselectivities (up to 90% enantiomeric excess (ee)). Different amine nucleophiles were applied in the reactions and the highest enantioselectivities were obtained for aniline and its analogues. Interestingly, some carbon nucleophiles could also be used and with indoles excellent ee values were obtained (up to 98%ee). The versatility of the propargylic amines obtained was demonstrated by their further elaboration to formal total syntheses of the antibiotic (+)-anisomycin and the cytokine modulator ()-cytoxazone.

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关键词：

asymmetric catalysis copper homogeneous catalysis propargylic substitution synthetic methods

DOI：

10.1002/chem.201003727

被引量：

197

年份：

2011