Enantioselective addition of methyl group to aldehydes catalyzed by titanium complex of fluorous ligand

Titanium complex of fluorous axially dissymmetric ligand ((Ra∗)-2,2′-bis[(R∗)-perfluoro-1H-1-hydroxyoctyl]biphenyl, ((Ra∗)-(R∗)2-1)) having perfluoroheptyl carbinol moieties catalyzed enantioselective addition of a methyl group to aldehydes. Dimethylzinc prepared in situ by mixing ZnCl2 and methyl magnesium bromide without removal of magnesium salt was more reactive for addition of methyl group than dimethylzinc without magnesium salt, and gave up to 99% ee of the products. The high fluorine content of 1 enables it to be recoverable by the selective extraction with perfluorohexane.