A series of new 1,1¢-bi-2-naphthol (BINOL) derived ligands, 3-[6-(hydroxymethyl)pyridin-2-yl]-BINOLs or 3,3¢-bis[6-(hydroxymethyl)pyridin-2-yl]-BINOLs, bearing one or two chiral pyridinylmethanols attached to a binaphthyl skeleton, have been synthesized using the Suzuki cross-coupling reaction. The resulting compounds have been used as ligands in the enantioselective addition of diethylzinc to aldehydes; the products were obtained with up to 96% ee.As an important C 2 -symmetric ligand, 1,1¢-bi-2-naphthol (BINOL) and its derivatives have been used extensively in asymmetric catalysis and chiral recognition and they also exhibit outstanding chiral induction in many processes. 1,2 In particular, BINOL derivatives bearing one or two chiral group at the 3-or 3,3¢-positions have presented high enantioselective catalysis activity in various enantioselective reactions such as oxidative coupling reactions, 3a-c 1,3-dipolar cycloadditions, 3d and sulfoxidations. 3e The introduction of a chiral group, utilizing natural resources such as amino acids and amino alcohols, has revealed interesting properties such as: (1) the stereogenic centers are adjustable (to give matched and mismatched combinations); (2) the steric effects are tunable (by modification of the R group, Scheme 1); (3) the effect of axial chirality of BINOL and chirality at the carbon center is also easily adjusted for good enantioselectivity.C 1 -Symmetric chiral pyridinylmethanols have been found extensive application 4 as chiral auxiliaries and ligands in asymmetric catalysis and can also be easily prepared by reaction of 2-lithiopyridine with optically active naturally occurring ketones, such as (-)-fenchone, (-)-camphor, and (-)-menthone. By introducing optically active pyridinylmethanols stemming from these naturally occurring ketones into the 3-or 3,3¢-positions of BINOLs, we expect to obtain a potentially useful chiral ligand for asymmetric synthesis.Our group has already reported the synthesis of BINOL ligands substituted by heteraromatic groups, such as 3-pyridinyl-BINOLs and 3,3¢-bis(pyridinyl)-BINOLs, by Suzuki cross-coupling reactions. 5 Herein, we report a series of BINOL derivatives with substituted by chiral groups, 3-[6-(hydroxymethyl)pyridin-2-yl]-BINOLs 9a-c or 3,3¢-bis[6-(hydroxymethyl)pyridin-2-yl]-BINOLs 8a-c that were also synthesized by Suzuki cross-coupling reactions of both enantiomeric forms of 3-(1,3,2-dioxaborolan-2-yl)-BINOLs 5 or 3,3¢-bis(1,3,2-dioxaborolan-2-yl)-BINOLs 4 with chiral 6-bromopyridin-2-ylmethanols 2a-c; their reactivity and enantioselectivity were tested in the enantioselective addition of diethylzinc to aldehydes.According to the known procedure, 4a the 6-bromopyridin-2-ylmethanols 2a-c were prepared by monolithiation of 2,6-dibromopyridine in diethyl ether followed by trapping with (-)-fenchone, (+)-camphor, or (-)-menthone (Scheme 1). Compounds 2a-c were obtained as single diastereomers according to NMR analysis of the product. The yields were 42-90% based on 2,6-dibromopyridine, depending mostly on the nature of...