Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size
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...
Published in: | Journal of the American Chemical Society |
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ftuniveindcris:oai:pure.tue.nl:publications/d97f3876-3eb0-422d-ba08-962a24186e9a 2024-04-28T08:02:01+00:00 Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size 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. 2007 https://research.tue.nl/en/publications/d97f3876-3eb0-422d-ba08-962a24186e9a https://doi.org/10.1021/ja071241a eng eng https://research.tue.nl/en/publications/d97f3876-3eb0-422d-ba08-962a24186e9a info:eu-repo/semantics/closedAccess 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 2007 , ' Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size ' , Journal of the American Chemical Society , vol. 129 , no. 23 , pp. 7393-7398 . https://doi.org/10.1021/ja071241a article 2007 ftuniveindcris https://doi.org/10.1021/ja071241a 2024-04-09T02:31:42Z 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%). Article in Journal/Newspaper Antarc* Antarctica Eindhoven University of Technology research portal Journal of the American Chemical Society 129 23 7393 7398 |
institution |
Open Polar |
collection |
Eindhoven University of Technology research portal |
op_collection_id |
ftuniveindcris |
language |
English |
description |
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%). |
format |
Article in Journal/Newspaper |
author |
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. |
spellingShingle |
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. Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
author_facet |
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. |
author_sort |
Buijtenen, van, J. |
title |
Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
title_short |
Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
title_full |
Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
title_fullStr |
Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
title_full_unstemmed |
Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
title_sort |
switching from s- to r-selectivity in the candida antarctica lipase b-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size |
publishDate |
2007 |
url |
https://research.tue.nl/en/publications/d97f3876-3eb0-422d-ba08-962a24186e9a https://doi.org/10.1021/ja071241a |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
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 2007 , ' Switching from S- to R-selectivity in the Candida antarctica lipase B-catalyzed ring-opening of omega-methylated lactones : tuning polymerizations by ring size ' , Journal of the American Chemical Society , vol. 129 , no. 23 , pp. 7393-7398 . https://doi.org/10.1021/ja071241a |
op_relation |
https://research.tue.nl/en/publications/d97f3876-3eb0-422d-ba08-962a24186e9a |
op_rights |
info:eu-repo/semantics/closedAccess |
op_doi |
https://doi.org/10.1021/ja071241a |
container_title |
Journal of the American Chemical Society |
container_volume |
129 |
container_issue |
23 |
container_start_page |
7393 |
op_container_end_page |
7398 |
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1797573518305525760 |