A New Synthetic Route to Enantiomerically Pure Axially Chiral 2,2‘-Bipyridine N,N‘-Dioxides. Highly Efficient Catalysts for Asymmetric Allylation of Aldehydes with Allyl(trichloro)silanes
- 17 July 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (16) , 6329-6337
- https://doi.org/10.1021/jo0300800
Abstract
New axially chiral 2,2‘-bipyridine N,N‘-dioxides 1 were obtained in an enantiomerically pure form by way of cyclic diesters 6 or 7 which were formed by the esterification of diols 2 with (R)-2,2‘-bis(chlorocarbonyl)-1,1‘-binaphthalene (5). Epimerization of the kinetic products at the ester formation (Rnap,Spyr)-6 to the thermodynamically stable isomers (Rnap,Rpyr)-7 was observed in refluxing toluene or in the presence of trifluoroacetic acid. One of the N,N‘-dioxides 1a which is substituted with phenyl groups at the 6 and 6‘ positions was found to be highly catalytically active and enantioselective for the asymmetric allylation of aldehydes with allyl(trichloro)silane giving homoallyl alcohols.Keywords
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