(+)-(2R,3E)-4-(benzo[d][1',3']dioxol-5'-yl)-but-3-en-2-ol

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (+)-(2R,3E)-4-(benzo[d][1',3']dioxol-5'-yl)-but-3-en-2-ol
• 英文别名: (E)-4-(benzo[d][1',3']-diox-5'-yl)but-3-en-2-ol；(R,E)-4-(benzo[d][1,3]dioxol-5-yl)but-3-en-2-ol；(E,2R)-4-(1,3-benzodioxol-5-yl)but-3-en-2-ol
• 化学式: C₁₁H₁₂O₃
• 分子量: 192.214
• InChiKey: BFKJEEFQRZRWBY-UFUPEUMYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(2R,3E)-4-(benzo[d][1',3']dioxol-5'-yl)-but-3-en-2-ol 在 丙酸 、 sodium hydroxide 作用下， 以 乙醇 为溶剂， 反应 27.0h， 生成 (+)-(3S,4E)-3-(benzo[d][1',3']dioxol-5'-yl)hex-4-enoic acid
  参考文献：
  名称：

  Chiral δ-iodo-γ-lactones derived from cuminaldehyde, 2,5-dimethylbenzaldehyde and piperonal: chemoenzymatic synthesis and antiproliferative activity

  摘要：

  Six enantiomeric pairs of beta-aryl-delta-iodo-gamma-lactones 8a-c, 9a-c derived from cuminaldehyde, 2,5-dimethylbenzaldehyde and piperonal were synthesized with high enantiomeric purities (ee 93-99%) from enantiomerically enriched allyl alcohols 3a-c. The key step in the synthesis of lactones 8a and 9a was the kinetic resolution of racemic (E)-4-(4'-isopropylphenyl)but-3-en-2-ol 3a by a lipase-catalysed transesterification. Among the five tested enzymes, the most effective and enantioselective was lipase B from Candida antarctica and after 2 h (-)-(S)-alcohol 3a and (+)-(R)-propionate 5 were obtained with ee's >= 99%. The transfer of chirality from alcohols (S)-3a-c and (R)-3a-c to gamma,delta-unsaturated esters (S)-6a-c and (R)-6a-c via a stereoselective Johnson-Claisen rearrangement followed by hydrolysis and iodolactonization afforded the final lactones 8a-c and 9a-c. The configurations of their stereogenic centres were assigned based on crystallographic analysis and/or the iodolactonization mechanism. In 42 of 48 tests, the synthesized lactones showed antiproliferative activity against four selected cancer lines (Jurkat, D17, GL-1, CLBL-1). The trans-stereoisomers were more active than the cis-stereoisomers and the highest activity was found for lactone (-)-trans-(4S,5R,6S)-9c with a 1,3-benzodioxole substituent and both enantiomers of the trans-lactone with a 2,5-dimethylphenyl substituent: (+)-9b and (-)-9b. Among the trans-lactones, those with a (4S,5R,6S)-configuration exhibited higher activity than their enantiomers and the most significant difference was observed for the enantiomers of the trans-lactone with a 1,3-benzodioxole substituent 9c (IC50 = 5.29 and 5.08 vs 36.47 and 33.77 for Jurkat and GL-1 cancer lines respectively). (C) 2016 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2016.02.003
• 作为产物：
  描述：

  (E)-4-(benzo[d][1',3']dioxol-5'-yl)-but-3-en-2-ol 在 Candida antarctica lipase immobilized on acrylic resin 、 sodium hydroxide 作用下， 以 乙醇 、 异丙醚 、 水 为溶剂， 反应 5.0h， 生成 (+)-(2R,3E)-4-(benzo[d][1',3']dioxol-5'-yl)-but-3-en-2-ol
  参考文献：
  名称：

  （E）-4-（2'，5'-二甲基苯基）-but-3-en-2-ol和（E）-4-（benzo [ d ] [1'，3'] dioxol-5的动力学拆分脂肪酶催化的酯交换反应合成'-基）-丁-3-烯-2-醇

  摘要：

  开发了一种短而有效的化学酶促途径，以生产两种立体异构形式的烯丙醇，其在立体异构中心具有庞大的芳族取代基，即（E）-4-（2'，5'-二甲基苯基）-but-3-en-2 -ol和（E）-4-（苯并[ d ] [1'，3']二恶醇-5'-基）-丁-3-烯-2-醇。醇经过脂肪酶催化的酯交换反应，南极假丝酵母（CAL-B）的脂肪酶被证明是筛选实验中最有效的生物催化剂，显示出对（R）-对映异构体的高度对映异构性。用乙酸异丙烯酯代替丙酸乙烯酯会降低所有脂肪酶催化的（E）-4-（苯并[ d]] [1'，3']二氧杂环戊烯-5'-基） -丁-3-烯-2-醇，但在CAL-B和Amano脂肪酶PS的两种制剂的情况下，对映选择率为显著增强（Ë > 100）。在（的制备规模反应ë）-4-（2'，5'-二甲基苯基） -丁-3-烯-2-醇与丙酸乙烯酯催化由CAL-B，未反应的（ - ） - （小号） -醇（EE = 98％）和（+）

  DOI：

  10.1016/j.tetasy.2015.05.006

文献信息

• Asymmetric 1,2-Reduction of Enones with Potassium Borohydride Catalyzed by Chiral <i>N,N</i>′-Dioxide–Scandium(III) Complexes
  作者：Peng He、Xiaohua Liu、Haifeng Zheng、Wei Li、Lili Lin、Xiaoming Feng

  DOI：10.1021/ol302430h

  日期：2012.10.5

  The first catalytic enantioselective 1,2-reduction of enones with 0.45 mol equiv potassium borohydride solution catalyzed by a chiral N,N′-dioxide–Sc(III) complex catalyst was accomplished under mild reaction conditions. A number of optically active allylic alcohols were obtained in good to excellent enantioselectivities (up to 95% ee) with nearly quantitative yields.

  在温和的反应条件下，用手性N，N'-二氧化物-Sc（III）络合物催化剂催化的0.45摩尔当量硼氢化钾溶液对烯酮的首次催化对映选择性1,2-还原。以接近定量的产率获得了许多具有良好至优异对映选择性（高达95％ee）的旋光烯丙基醇。
• Chemoenzymatic Synthesis of trans-β-Aryl-δ-hydroxy-γ-lactones and Enzymatic Kinetic Resolution of Their Racemic Mixtures
  作者：Andrzej Skrobiszewski、Witold Gładkowski、Gabriela Maciejewska、Czesław Wawrzeńczyk

  DOI：10.3390/molecules21111552

  日期：——

  m-chloroperbenzoic acid (m-CPBA). An alternative method for the production of optically active trans-β-aryl-δ-hydroxy-γ-lactones 5a–d was lipase-catalyzed kinetic resolution of their racemic mixtures by transesterification with vinyl propionate as the acyl donor. The most efficient enzyme in the screening procedure was lipase B from Candida antarctica. Its application on a preparative scale after 6 h afforded unreacted

  开发了两种新颖方便的途径来获得对映异构体富集的反式-β-芳基-δ-羟基-γ-内酯 5a-d，具有潜在的拒食和抗癌活性。在第一种方法中，从衍生自酶分解烯丙醇 1a-d 的 γ,δ-不饱和酯 4a-d 的相应对映体开始，羟基内酯 5a-d 的两种对映体都以高对映体过量（73%-97%）合成。基于在间氯过苯甲酸 (m-CPBA) 存在下酯 4a-d 的酸性内酯化机制，对合成化合物的立体中心的构型进行了分配。生产光学活性反式-β-芳基-δ-羟基-γ-内酯 5a-d 的另一种方法是脂肪酶催化的外消旋混合物的动力学拆分，通过与丙酸乙烯酯作为酰基供体进行酯交换。筛选程序中最有效的酶是来自南极念珠菌的脂肪酶 B。它在 6 小时后以制备规模应用得到未反应的 (+)-(4S,5R,6S)-羟基内酯 5a-d 和 (+)-(4R,5S,6R)-丙酸酯 6a-d，其中大部分具有高对映体过量 (92%–98%)。内酯
• Chiral δ-iodo-γ-lactones derived from cuminaldehyde, 2,5-dimethylbenzaldehyde and piperonal: chemoenzymatic synthesis and antiproliferative activity
  作者：Witold Gładkowski、Andrzej Skrobiszewski、Marcelina Mazur、Anna Gliszczyńska、Marta Czarnecka、Aleksandra Pawlak、Bożena Obmińska-Mrukowicz、Gabriela Maciejewska、Agata Białońska

  DOI：10.1016/j.tetasy.2016.02.003

  日期：2016.4

  Six enantiomeric pairs of beta-aryl-delta-iodo-gamma-lactones 8a-c, 9a-c derived from cuminaldehyde, 2,5-dimethylbenzaldehyde and piperonal were synthesized with high enantiomeric purities (ee 93-99%) from enantiomerically enriched allyl alcohols 3a-c. The key step in the synthesis of lactones 8a and 9a was the kinetic resolution of racemic (E)-4-(4'-isopropylphenyl)but-3-en-2-ol 3a by a lipase-catalysed transesterification. Among the five tested enzymes, the most effective and enantioselective was lipase B from Candida antarctica and after 2 h (-)-(S)-alcohol 3a and (+)-(R)-propionate 5 were obtained with ee's >= 99%. The transfer of chirality from alcohols (S)-3a-c and (R)-3a-c to gamma,delta-unsaturated esters (S)-6a-c and (R)-6a-c via a stereoselective Johnson-Claisen rearrangement followed by hydrolysis and iodolactonization afforded the final lactones 8a-c and 9a-c. The configurations of their stereogenic centres were assigned based on crystallographic analysis and/or the iodolactonization mechanism. In 42 of 48 tests, the synthesized lactones showed antiproliferative activity against four selected cancer lines (Jurkat, D17, GL-1, CLBL-1). The trans-stereoisomers were more active than the cis-stereoisomers and the highest activity was found for lactone (-)-trans-(4S,5R,6S)-9c with a 1,3-benzodioxole substituent and both enantiomers of the trans-lactone with a 2,5-dimethylphenyl substituent: (+)-9b and (-)-9b. Among the trans-lactones, those with a (4S,5R,6S)-configuration exhibited higher activity than their enantiomers and the most significant difference was observed for the enantiomers of the trans-lactone with a 1,3-benzodioxole substituent 9c (IC50 = 5.29 and 5.08 vs 36.47 and 33.77 for Jurkat and GL-1 cancer lines respectively). (C) 2016 Elsevier Ltd. All rights reserved.
• Kinetic resolution of (E)-4-(2′,5′-dimethylphenyl)-but-3-en-2-ol and (E)-4-(benzo[d][1′,3′]dioxol-5′-yl)-but-3-en-2-ol through lipase-catalyzed transesterification
  作者：Witold Gładkowski、Anna Gliszczyńska、Monika Siepka、Marta Czarnecka、Gabriela Maciejewska

  DOI：10.1016/j.tetasy.2015.05.006

  日期：2015.7

  respectively. The kinetic resolution of (E)-4-(benzo[d][1′,3′]dioxol-5′-yl)-but-3-en-2-ol using isopropenyl acetate and CAL-B after 1 h gave (−)-(S)-alcohol (ee = 99%) and (+)-(R)-acetate (ee = 91%) in yields of 44% and 46%, respectively. (+)-(R)-Alcohols were obtained by the hydrolysis of the corresponding esters. Except for (+)-(R,E)-4-(benzo[d][1′,3′]dioxol-5′-yl)-but-3-en-2-ol, all enantiomerically

  开发了一种短而有效的化学酶促途径，以生产两种立体异构形式的烯丙醇，其在立体异构中心具有庞大的芳族取代基，即（E）-4-（2'，5'-二甲基苯基）-but-3-en-2 -ol和（E）-4-（苯并[ d ] [1'，3']二恶醇-5'-基）-丁-3-烯-2-醇。醇经过脂肪酶催化的酯交换反应，南极假丝酵母（CAL-B）的脂肪酶被证明是筛选实验中最有效的生物催化剂，显示出对（R）-对映异构体的高度对映异构性。用乙酸异丙烯酯代替丙酸乙烯酯会降低所有脂肪酶催化的（E）-4-（苯并[ d]] [1'，3']二氧杂环戊烯-5'-基） -丁-3-烯-2-醇，但在CAL-B和Amano脂肪酶PS的两种制剂的情况下，对映选择率为显著增强（Ë > 100）。在（的制备规模反应ë）-4-（2'，5'-二甲基苯基） -丁-3-烯-2-醇与丙酸乙烯酯催化由CAL-B，未反应的（ - ） - （小号） -醇（EE = 98％）和（+）