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...
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ftuniveindhoven:oai:library.tue.nl:640916 2023-05-15T13:56:31+02:00 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, J Jeroen van As, BAC Bart van Verbruggen, M Marloes Roumen, L Luc Vekemans, JAJM Jef = Jozef Pieterse, K Koen Hilbers, PAJ Peter Hulshof, LA Bert Palmans, ARA Anja Meijer, EW Bert 2007 application/pdf http://repository.tue.nl/640916 en eng Copyright (c) Buijtenen, J Jeroen van Copyright (c) As, BAC Bart van Copyright (c) Verbruggen, M Marloes Copyright (c) Roumen, L Luc Copyright (c) Vekemans, JAJM Jef = Jozef Copyright (c) Pieterse, K Koen Copyright (c) Hilbers, PAJ Peter Copyright (c) Hulshof, LA Bert Copyright (c) Palmans, ARA Anja Copyright (c) Meijer, EW Bert ISSN:0002-7863 Article / Letter to the editor 2007 ftuniveindhoven 2018-12-26T13:34:47Z 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 (TU/e): Research Portal |
institution |
Open Polar |
collection |
Eindhoven University of Technology (TU/e): Research Portal |
op_collection_id |
ftuniveindhoven |
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, J Jeroen van As, BAC Bart van Verbruggen, M Marloes Roumen, L Luc Vekemans, JAJM Jef = Jozef Pieterse, K Koen Hilbers, PAJ Peter Hulshof, LA Bert Palmans, ARA Anja Meijer, EW Bert |
spellingShingle |
Buijtenen, J Jeroen van As, BAC Bart van Verbruggen, M Marloes Roumen, L Luc Vekemans, JAJM Jef = Jozef Pieterse, K Koen Hilbers, PAJ Peter Hulshof, LA Bert Palmans, ARA Anja Meijer, EW Bert 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, J Jeroen van As, BAC Bart van Verbruggen, M Marloes Roumen, L Luc Vekemans, JAJM Jef = Jozef Pieterse, K Koen Hilbers, PAJ Peter Hulshof, LA Bert Palmans, ARA Anja Meijer, EW Bert |
author_sort |
Buijtenen, J Jeroen van |
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 |
http://repository.tue.nl/640916 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
ISSN:0002-7863 |
op_rights |
Copyright (c) Buijtenen, J Jeroen van Copyright (c) As, BAC Bart van Copyright (c) Verbruggen, M Marloes Copyright (c) Roumen, L Luc Copyright (c) Vekemans, JAJM Jef = Jozef Copyright (c) Pieterse, K Koen Copyright (c) Hilbers, PAJ Peter Copyright (c) Hulshof, LA Bert Copyright (c) Palmans, ARA Anja Copyright (c) Meijer, EW Bert |
_version_ |
1766264023880302592 |