Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid
Abstract Both enantiomers of 2‐ tert ‐butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) acid, which has a unique quaternary chiral center located on the acetal carbon, were prepared from a racemic ketone in which the carboxy group was replaced by a trifluoroacetyl group. First, reduction with fung...
Published in: | Advanced Synthesis & Catalysis |
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crwiley:10.1002/adsc.201000446 2024-06-02T07:57:09+00:00 Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid Higashi, Toshinori Abe, Chika Ninomiya, Keiko Machida, Takuya Chishima, Nobuyuki Taketomi, Shohei Furuta, Miyu Komaki, Yoko Senba, Yoshihiko Tokuda, Taeko Shoji, Mitsuru Sugai, Takeshi 2010 http://dx.doi.org/10.1002/adsc.201000446 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201000446 https://onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201000446 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Advanced Synthesis & Catalysis volume 352, issue 14-15, page 2549-2558 ISSN 1615-4150 1615-4169 journal-article 2010 crwiley https://doi.org/10.1002/adsc.201000446 2024-05-03T11:44:14Z Abstract Both enantiomers of 2‐ tert ‐butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) acid, which has a unique quaternary chiral center located on the acetal carbon, were prepared from a racemic ketone in which the carboxy group was replaced by a trifluoroacetyl group. First, reduction with fungi, Geotrichum candidum provided (2 S ,1′ S )‐ and (2 R ,1′ S )‐ 1′‐(2‐ tert ‐butyl‐2‐methyl‐1,3‐benzodioxol‐4‐yl)‐2′,2′,2′‐trifluoroethanol in a highly enantiofacially selective manner. After acetylation, the resulting diastereomeric mixture was submitted to Candida antarctica lipase B‐catalyzed transesterification. The reaction proceeded in a stereoselective manner under the influence of the chiral center at the acetal carbon, even though it was six atoms removed from the ester carbonyl carbon. Although the two substrates had the same absolute configuration at the secondary alcohol, the reaction rate of one stereoisomer was 72 times greater than that of the other isomer. The reason for this differential reactivity was attributed mainly to a large difference in V max(app) between the stereoisomers. The products, acetate and alcohol, were easily separated by chromatography, and each was then derivatized to ( R )‐ and ( S )‐TBMB acid, with >99.2% ee , respectively. Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library Advanced Synthesis & Catalysis 352 14-15 2549 2558 |
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Wiley Online Library |
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English |
description |
Abstract Both enantiomers of 2‐ tert ‐butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) acid, which has a unique quaternary chiral center located on the acetal carbon, were prepared from a racemic ketone in which the carboxy group was replaced by a trifluoroacetyl group. First, reduction with fungi, Geotrichum candidum provided (2 S ,1′ S )‐ and (2 R ,1′ S )‐ 1′‐(2‐ tert ‐butyl‐2‐methyl‐1,3‐benzodioxol‐4‐yl)‐2′,2′,2′‐trifluoroethanol in a highly enantiofacially selective manner. After acetylation, the resulting diastereomeric mixture was submitted to Candida antarctica lipase B‐catalyzed transesterification. The reaction proceeded in a stereoselective manner under the influence of the chiral center at the acetal carbon, even though it was six atoms removed from the ester carbonyl carbon. Although the two substrates had the same absolute configuration at the secondary alcohol, the reaction rate of one stereoisomer was 72 times greater than that of the other isomer. The reason for this differential reactivity was attributed mainly to a large difference in V max(app) between the stereoisomers. The products, acetate and alcohol, were easily separated by chromatography, and each was then derivatized to ( R )‐ and ( S )‐TBMB acid, with >99.2% ee , respectively. |
format |
Article in Journal/Newspaper |
author |
Higashi, Toshinori Abe, Chika Ninomiya, Keiko Machida, Takuya Chishima, Nobuyuki Taketomi, Shohei Furuta, Miyu Komaki, Yoko Senba, Yoshihiko Tokuda, Taeko Shoji, Mitsuru Sugai, Takeshi |
spellingShingle |
Higashi, Toshinori Abe, Chika Ninomiya, Keiko Machida, Takuya Chishima, Nobuyuki Taketomi, Shohei Furuta, Miyu Komaki, Yoko Senba, Yoshihiko Tokuda, Taeko Shoji, Mitsuru Sugai, Takeshi Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid |
author_facet |
Higashi, Toshinori Abe, Chika Ninomiya, Keiko Machida, Takuya Chishima, Nobuyuki Taketomi, Shohei Furuta, Miyu Komaki, Yoko Senba, Yoshihiko Tokuda, Taeko Shoji, Mitsuru Sugai, Takeshi |
author_sort |
Higashi, Toshinori |
title |
Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid |
title_short |
Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid |
title_full |
Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid |
title_fullStr |
Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid |
title_full_unstemmed |
Chemoenzymatic Synthesis of Both Enantiomers of 2‐tert‐Butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (TBMB) Acid |
title_sort |
chemoenzymatic synthesis of both enantiomers of 2‐tert‐butyl‐2‐methyl‐1,3‐benzodioxole‐4‐carboxylic (tbmb) acid |
publisher |
Wiley |
publishDate |
2010 |
url |
http://dx.doi.org/10.1002/adsc.201000446 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.201000446 https://onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.201000446 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
Advanced Synthesis & Catalysis volume 352, issue 14-15, page 2549-2558 ISSN 1615-4150 1615-4169 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/adsc.201000446 |
container_title |
Advanced Synthesis & Catalysis |
container_volume |
352 |
container_issue |
14-15 |
container_start_page |
2549 |
op_container_end_page |
2558 |
_version_ |
1800739193816612864 |