Requirements for the formation of a chiral template.
The chemisorptive enantioselectivity of propylene oxide is examined on Pd(111) surfaces templated by chiral 2-methylbutanoate and 2-aminobutanoate species. It has been found previously that chiral propylene oxide is chemisorbed enantiospecifically onto Pd(111) surfaces modified by either (R)- or (S)-2-butoxide. The enantiomeric excess (ee) varied with template coverage, reaching a maximum of approximately 31%. Templating the surface using 2-methylbutanoate, where the chiral center is identical to that in the 2-butoxide species, but is now anchored to the surface by a carboxylate rather than an alkoxide linkage, shows no enantiospecificity. The enantioselectivity is restored when the methyl group is replaced by an amine group, where a maximum ee value of approximately 27% is found. DFT calculations and infrared measurements suggest that the structures of the butyl group on the surface are similar for both 2-butoxide and 2-methylbutanoate species, implying that gross conformational changes are not responsible for differences in chemisorptive enantioselectivity. There is no clear correlation between the location of the chiral center and enantioselectivity, suggesting that differences in the template adsorption site are also not responsible for the lack of enantioselectivity. It is proposed that the 2-butyl group in 2-methylbutanoate species is less rigidly bonded to the surface than that in 2-butoxides, allowing the chiral center to rotate azimuthally. It is postulated that the role of the amino group in 2-aminobutanoate species is to anchor the chiral group to the surface to inhibit azimuthal rotation.
Stacchiola
D
D
Department of Chemistry and Physics and Laboratory for Surface Studies, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53211, USA.
Burkholder
L
L
Zheng
T
T
Weinert
M
M
Tysoe
W T
WT
D000327:Adsorption; D000613:Aminobutyrates / Q000737:chemistry*; D002087:Butyrates / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D008956:Models, Chemical; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D013499:Surface Properties; D013696:Temperature
D000613:Aminobutyrates; D002087:Butyrates; D004852:Epoxy Compounds; D010165:Palladium; C012223:alpha-aminobutyric acid; C019475:2-methylbutanoic acid; C009068:propylene oxide