( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution
Abstract The best reaction condition of Candida antartica lipase B as biocatalyst, 3‐(2‐pyridyl)pyrazole as leaving azole, and water‐saturated methyl t ‐butyl ether as reaction medium at 45°C were first selected for performing the hydrolytic resolution of ( R , S )‐2‐(4‐chlorophenoxyl) azolides ( 1...
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crwiley:10.1002/chir.21024 2024-06-02T07:58:47+00:00 ( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution Kao, Min‐fang Lu, Pei‐yu Kao, Jou‐yan Wang, Pei‐yun Wu, An‐chi Tsai, Shau‐Wei 2011 http://dx.doi.org/10.1002/chir.21024 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchir.21024 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chir.21024 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Chirality volume 24, issue 1, page 60-66 ISSN 0899-0042 1520-636X journal-article 2011 crwiley https://doi.org/10.1002/chir.21024 2024-05-03T11:29:41Z Abstract The best reaction condition of Candida antartica lipase B as biocatalyst, 3‐(2‐pyridyl)pyrazole as leaving azole, and water‐saturated methyl t ‐butyl ether as reaction medium at 45°C were first selected for performing the hydrolytic resolution of ( R , S )‐2‐(4‐chlorophenoxyl) azolides ( 1 , 2 , 3 , 4 ). In comparison with the kinetic resolution of ( R , S )‐2‐phenylpropionyl 3‐(2‐pyridyl)pyrazolide or ( R , S )‐α‐methoxyphenylacetyl 3‐(2‐pyridyl)pyrazolide at the same reaction condition, excellent enantioselectivity with more than two order‐of‐magnitudes higher activity for each enantiomer was obtained. The resolution was then extended to other ( R , S )‐3‐(2‐pyridyl)pyrazolides ( 5 , 6 , 7 ) containing 2‐chloro, 3‐chloro, or 2,4‐dichloro substituent, giving good ( E > 48) to excellent ( E > 100) enantioselectivity. The thermodynamic analysis for 1 , 2 , and 4 , 5 , 6 , 7 demonstrates profound effects of the acyl or leaving moiety on varying enthalpic and entropic contributions to the difference of Gibbs free energies. A thorough kinetic analysis further indicates that on the basis of 6 , the excellent enantiomeric ratio for 4 and 7 is due to the higher reactivity of (S)‐ 4 and lower reactivity of (R)‐ 7 , respectively. Chirality 2011. © 2011 Wiley‐Liss, Inc. Article in Journal/Newspaper antartic* Wiley Online Library Chirality 24 1 60 66 |
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English |
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Abstract The best reaction condition of Candida antartica lipase B as biocatalyst, 3‐(2‐pyridyl)pyrazole as leaving azole, and water‐saturated methyl t ‐butyl ether as reaction medium at 45°C were first selected for performing the hydrolytic resolution of ( R , S )‐2‐(4‐chlorophenoxyl) azolides ( 1 , 2 , 3 , 4 ). In comparison with the kinetic resolution of ( R , S )‐2‐phenylpropionyl 3‐(2‐pyridyl)pyrazolide or ( R , S )‐α‐methoxyphenylacetyl 3‐(2‐pyridyl)pyrazolide at the same reaction condition, excellent enantioselectivity with more than two order‐of‐magnitudes higher activity for each enantiomer was obtained. The resolution was then extended to other ( R , S )‐3‐(2‐pyridyl)pyrazolides ( 5 , 6 , 7 ) containing 2‐chloro, 3‐chloro, or 2,4‐dichloro substituent, giving good ( E > 48) to excellent ( E > 100) enantioselectivity. The thermodynamic analysis for 1 , 2 , and 4 , 5 , 6 , 7 demonstrates profound effects of the acyl or leaving moiety on varying enthalpic and entropic contributions to the difference of Gibbs free energies. A thorough kinetic analysis further indicates that on the basis of 6 , the excellent enantiomeric ratio for 4 and 7 is due to the higher reactivity of (S)‐ 4 and lower reactivity of (R)‐ 7 , respectively. Chirality 2011. © 2011 Wiley‐Liss, Inc. |
format |
Article in Journal/Newspaper |
author |
Kao, Min‐fang Lu, Pei‐yu Kao, Jou‐yan Wang, Pei‐yun Wu, An‐chi Tsai, Shau‐Wei |
spellingShingle |
Kao, Min‐fang Lu, Pei‐yu Kao, Jou‐yan Wang, Pei‐yun Wu, An‐chi Tsai, Shau‐Wei ( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
author_facet |
Kao, Min‐fang Lu, Pei‐yu Kao, Jou‐yan Wang, Pei‐yun Wu, An‐chi Tsai, Shau‐Wei |
author_sort |
Kao, Min‐fang |
title |
( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
title_short |
( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
title_full |
( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
title_fullStr |
( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
title_full_unstemmed |
( R, S)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
title_sort |
( r, s)‐2‐chlorophenoxyl pyrazolides as novel substrates for improving lipase‐catalyzed hydrolytic resolution |
publisher |
Wiley |
publishDate |
2011 |
url |
http://dx.doi.org/10.1002/chir.21024 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchir.21024 https://onlinelibrary.wiley.com/doi/pdf/10.1002/chir.21024 |
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antartic* |
genre_facet |
antartic* |
op_source |
Chirality volume 24, issue 1, page 60-66 ISSN 0899-0042 1520-636X |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/chir.21024 |
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Chirality |
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24 |
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1 |
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60 |
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66 |
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1800742312968454144 |