Modification of the Atropisomeric N,N-Ligand 2,2'-Di(pyridin-2-yl)-1,1'-binaphthalene and Its Application to the Asymmetric Allylation of Benzaldehyde

The atropisomeric compound 2,2'-di(pyridin-2-yl)-1,1'-binaphthalene (1) has been chlorinated, via its bis-N-oxide 2, at the 4 and 6 pyridine ring positions so as to generate the three isomeric species: 2,2'-bis(6-chloropyridin-2-yl)- (3a), 2-(4-chloropyridin-2-yl)-2'-(6-chloropyridin-2-yl)- (3b) and 2,2'-bis(4-chloropyridin-2-yl)-1,1'-binaphthalene (3c). The dichlorinated compounds underwent Ni-catalysed Kumada cross-coupling with MeMgI to give the methylated pyridine isomers: 2,2'-bis(6-methylpyridin-2-yl)- (4a), 2-(4-methylpyridin-2-yl)-2'-(6-methylpyridin-2-yl)- (4b) and 2,2'-bis(4-methylpyridin-2-yl)-1,1'-binaphthalene (4c). The enantiomerically pure forms of the six novel ligands (3a-3c and 4a-4c), prepared from enantiomerically pure 2,2'-di(pyridin-2-yl)-1,1'-binaphthalene (1), were tested in asymmetric catalysis, but proved to be no better and in most cases poorer than parent 1. The coordination of the ligands to Zn and Pd fragments has been explored and compared with the parent compound 1 so as to rationalise the negative effect of pyridine substitution on asymmetric induction in the zinc-catalysed allylation of benzaldehyde.