Syntheses and crystal structures of chiral BINOL derivatives and their applications in enantioselective lewis acid catalyzed addition of diethylzinc to aldehydes

Two novel chiral BINOL derivatives with bis(benzylamine) groups at the 3,3positions ;have been synthesized through the condensation reaction between 2,2'-bis(methoxymethyleneoxy)-1,1'-binaphthyl-3,3'-dicarboxylic acid and benzylamine or N-phenyl benzylamine in the presence of triethylamine. Suitable single crystal of (R)-NA'-dibenzyl-2,2'-dihydroxy-1, 1'-binaphthly-3,3'-diformamide (R)-3 for X-ray diffraction was obtained by recrystallization at room temperature from the mixture solvents. Crystallographic data of (R)-3: C40H36N2O6, M-r = 640.71, monoclinic, space group P2(1), a = 6.746(3), b = 21.883(9), c = 11.723(5) angstrom, beta = 104.605(7)degrees, Z = 2, V = 1674.7(12) A(3), D-c = 1.271 g/cm(3), F(000) = 676, R = 0.0729, wR = 0.1687 and mu(MoK alpha) = 0.086 mm(-1). Two chiral BINOL ligands were found to be effective in the enantioselective addition of diethylzinc to aldehydes and much different enantioselectivity was observed both in the presence and absence of Ti((OPr)-Pr-i)(4) In the former case, (R)-3 showed moderate enantioselectivity, which was lower than that of (R)-BINOL's; and in the latter case, (R)-4 gave the highest enantioselectivity up to 93.3% ee.*