Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size

• Published in: Journal of the American Chemical Society
• Main Authors: Buijtenen, van, J., As, van, B.A.C., Verbruggen, M., Roumen, L., Vekemans, J.A.J.M., Pieterse, K., Hilbers, P.A.J., Hulshof, L.A., Palmans, A.R.A., Meijer, E.W.
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2007
• Subjects: Antarc*; Antarctica
• Online Access: https://research.tue.nl/en/publications/d97f3876-3eb0-422d-ba08-962a24186e9a; https://doi.org/10.1021/ja071241a

Novozym 435-catalyzed ring-opening of a range of w-methylated lactones demonstrates fascinating differences in rate of reaction and enantioselectivity. A switch from S- to R-selectivity was obsd. upon going from small (ring sizes ?7) to large lactones (ring sizes >=8). This was attributed to the transition from a cisoid to a transoid conformational preference of the ester bond on going from small to large lactones. The S-selectivity of the ring-opening of the small, cisoid lactones was low to moderate, while the R-selectivity of the ring-opening of the large transoid lactones was surprisingly high. The S-selectivity of the ring-opening of the small, cisoid lactones combined with the established R-selectivity of the transesterification of (aliph.) secondary alcs. prevented polymn. from taking place. Ring-opening of the large, transoid lactones was R-selective with high enantioselectivity. As a result, these lactones could be polymd., without exception, by straightforward kinetic resoln. polymn., yielding the enantiopure R-polyester with excellent enantiomeric excess (>99%).