Phosphoramidite ligands are widely used in catalysisa nd normally constructed from large C 2symmetrical diols such as BINOL or TADDOL.W e report here on new ligands based on as et of simple diols that had been previously overlooked. Ligands based on (S,S)-trans-cyclohexanediol and( R,R)-(+ +)-1,2-diphenyl-1,2-ethanediol, in combination with both chiral anda chiral amines,w ere tested in 3d ifferent copper-catalyzed asymmetric reactions and up to 89% ee was observed. Ad ifferent ligandg avet he best results in each reactione xamined.U sing mesocis-cyclohexanediol and meso-cis-diphenyl-1,2-ethanediol with ac hiral non-racemic amine gave diastereomeric ligands bearing achirotopics tereogenic phosphorus atoms which were characterized with the assistance of X-ray crystallography and variablet emperature NMRs tudies.T his workp rovides an ew set of ligands that may be useful in some asymmetric reactions when phosphoramidites based on BINOL and TADDOL are ineffective. We also identify an ovels tereochemical feature of phosphoramidites that may be useful in asymmetric catalysis and ligand design.

Here we report a rhodium-catalyzed asymmetric carboxylation of ester-containing allylic bromides to form stereogenic carbon centers bearing two different carboxylates with high yields and enantioselectivities.