書誌事項
- タイトル別名
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- Hydrolase-Catalyzed Kinetic Resolutions of Chiral Alcohols. Mechanistic Study on the Origin of the Enantioselectivity.
- カスイ ブンカイ コウソ オ モチイタ フセイ アルコール ノ ソクドロンテキ コウガク ブンカツ エナンチオ センタクセイ ノ ハツゲン キコウ
- Mechanistic Study on the Origin of the Enantioselectivity
- エナンチオ選択性の発現機構
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抄録
Mechanistic studies on the enantioselectivity in the hydrolase-catalyzed kinetic resolutions of racemic alcohols are described. Based on kinetic measurements, molecular orbital calculations and computer modeling with X-ray crystal structures of several lipases, we proposed the transition-state model that is consistent with the experimental observations such as (i) high enantioselectivity, (ii) broad substrate specificity and (iii) an empirical rule (R-preference for secondary alcohols). A large secondary alcohol having a tetraphenylporphyrin as the substituent was successfully resolved by several lipases, demonstrating the validity of our transition-state model. The S-preference of subtilisins for secondary alcohols was rationalized by applying the protocol used in the transition-state model for lipases to subtilisins. We also found that the lipasecatalyzed transesterifications of chiral alcohols in organic solvents can proceed even at -40°C. Interestingly, theE value increased with decreasing temperature, and a linear relationship was observed between In E and 1/T, from which the ΔΔH‡and ΔΔS‡ values were calculated. These thermodynamic parameters were useful for investigating the mechanism of the enantioselectivity of the hydrolases toward chiral alcohols.
収録刊行物
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- 有機合成化学協会誌
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有機合成化学協会誌 58 (7), 691-698, 2000
公益社団法人 有機合成化学協会
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詳細情報 詳細情報について
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- CRID
- 1390001205276536448
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- NII論文ID
- 10008820998
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- NII書誌ID
- AN0024521X
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- ISSN
- 18836526
- 00379980
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- NDL書誌ID
- 5397721
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- 本文言語コード
- ja
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- データソース種別
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- JaLC
- NDL
- Crossref
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- 抄録ライセンスフラグ
- 使用不可