An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins
Abstract A one‐pot chemo‐enzymatic synthesis of highly enantiomerically enriched O ‐acetylcyanohydrins has been developed. The bimetallic (salen)titanium complex 1 is used to convert aldehydes into nonracemic ( R )‐ O ‐acetylcyanohydrins with 61 to 93 % enantiomeric excess. A lipase enzyme is then u...
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crwiley:10.1002/ejoc.200600467 2024-04-07T07:47:33+00:00 An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins Belokon, Yuri N. Blacker, A. John Clutterbuck, Lisa A. Hogg, David North, Michael Reeve, Christopher 2006 http://dx.doi.org/10.1002/ejoc.200600467 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fejoc.200600467 https://onlinelibrary.wiley.com/doi/full/10.1002/ejoc.200600467 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor European Journal of Organic Chemistry volume 2006, issue 20, page 4609-4617 ISSN 1434-193X 1099-0690 Organic Chemistry Physical and Theoretical Chemistry journal-article 2006 crwiley https://doi.org/10.1002/ejoc.200600467 2024-03-08T03:51:47Z Abstract A one‐pot chemo‐enzymatic synthesis of highly enantiomerically enriched O ‐acetylcyanohydrins has been developed. The bimetallic (salen)titanium complex 1 is used to convert aldehydes into nonracemic ( R )‐ O ‐acetylcyanohydrins with 61 to 93 % enantiomeric excess. A lipase enzyme is then used to hydrolyse the unwanted ( S ) enantiomer of the product, leaving ( R )‐ O ‐acetylcyanohydrins with 80 to >99 % enantiomeric excess and in 75 to 96 % overall yield. Of ten lipase enzymes investigated, Candida antarctica lipase‐B (CAL‐B) has been shown to be the most suitable and the conditions for its use have been optimised. Although no single solvent has been found in which both catalyst 1 and CAL‐B gave high reaction rates and enantioselectivities, two procedures to allow their sequential use without purification of the O ‐acetylcyanohydrin produced by catalyst 1 have been developed. In the first of these, the reaction with catalyst 1 is carried out in dichloromethane which is then removed and replaced with methyl tert ‐butyl ether prior to addition of the enzyme. In the second procedure, the first reaction is carried out in concentrated dichloromethane solution, and this is then just diluted with methyl tert ‐butyl ether prior to addition of the lipase. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library Salen ENVELOPE(25.467,25.467,-72.133,-72.133) European Journal of Organic Chemistry 2006 20 4609 4617 |
institution |
Open Polar |
collection |
Wiley Online Library |
op_collection_id |
crwiley |
language |
English |
topic |
Organic Chemistry Physical and Theoretical Chemistry |
spellingShingle |
Organic Chemistry Physical and Theoretical Chemistry Belokon, Yuri N. Blacker, A. John Clutterbuck, Lisa A. Hogg, David North, Michael Reeve, Christopher An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins |
topic_facet |
Organic Chemistry Physical and Theoretical Chemistry |
description |
Abstract A one‐pot chemo‐enzymatic synthesis of highly enantiomerically enriched O ‐acetylcyanohydrins has been developed. The bimetallic (salen)titanium complex 1 is used to convert aldehydes into nonracemic ( R )‐ O ‐acetylcyanohydrins with 61 to 93 % enantiomeric excess. A lipase enzyme is then used to hydrolyse the unwanted ( S ) enantiomer of the product, leaving ( R )‐ O ‐acetylcyanohydrins with 80 to >99 % enantiomeric excess and in 75 to 96 % overall yield. Of ten lipase enzymes investigated, Candida antarctica lipase‐B (CAL‐B) has been shown to be the most suitable and the conditions for its use have been optimised. Although no single solvent has been found in which both catalyst 1 and CAL‐B gave high reaction rates and enantioselectivities, two procedures to allow their sequential use without purification of the O ‐acetylcyanohydrin produced by catalyst 1 have been developed. In the first of these, the reaction with catalyst 1 is carried out in dichloromethane which is then removed and replaced with methyl tert ‐butyl ether prior to addition of the enzyme. In the second procedure, the first reaction is carried out in concentrated dichloromethane solution, and this is then just diluted with methyl tert ‐butyl ether prior to addition of the lipase. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) |
format |
Article in Journal/Newspaper |
author |
Belokon, Yuri N. Blacker, A. John Clutterbuck, Lisa A. Hogg, David North, Michael Reeve, Christopher |
author_facet |
Belokon, Yuri N. Blacker, A. John Clutterbuck, Lisa A. Hogg, David North, Michael Reeve, Christopher |
author_sort |
Belokon, Yuri N. |
title |
An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins |
title_short |
An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins |
title_full |
An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins |
title_fullStr |
An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins |
title_full_unstemmed |
An Asymmetric, Chemo‐Enzymatic Synthesis of O ‐Acetylcyanohydrins |
title_sort |
asymmetric, chemo‐enzymatic synthesis of o ‐acetylcyanohydrins |
publisher |
Wiley |
publishDate |
2006 |
url |
http://dx.doi.org/10.1002/ejoc.200600467 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fejoc.200600467 https://onlinelibrary.wiley.com/doi/full/10.1002/ejoc.200600467 |
long_lat |
ENVELOPE(25.467,25.467,-72.133,-72.133) |
geographic |
Salen |
geographic_facet |
Salen |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
European Journal of Organic Chemistry volume 2006, issue 20, page 4609-4617 ISSN 1434-193X 1099-0690 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/ejoc.200600467 |
container_title |
European Journal of Organic Chemistry |
container_volume |
2006 |
container_issue |
20 |
container_start_page |
4609 |
op_container_end_page |
4617 |
_version_ |
1795674686588190720 |