(+)-(2R,3E)-4-(4'-isopropylphenyl)but-3-en-2-ol

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+)-(2R,3E)-4-(4'-isopropylphenyl)but-3-en-2-ol
• 英文别名: (R,E)-4-(4-isopropylphenyl)but-3-en-2-ol；(E,2R)-4-(4-propan-2-ylphenyl)but-3-en-2-ol
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: SLVGTZHVTFYEFE-SGUJLRQBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+)-(2R,3E)-4-(4'-isopropylphenyl)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 (-)-(3R,4E)-3-(4'-isopropylphenyl)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：

  4-(4-异丙基苯基)-3-丁烯-2-酮 在 sodium tetrahydroborate 、 lipase B from Candida antartica 、 sodium hydroxide 作用下， 以 甲醇 、 乙醇 、 异丙醚 为溶剂， 反应 8.0h， 生成 (+)-(2R,3E)-4-(4'-isopropylphenyl)but-3-en-2-ol
  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

文献信息

• Accessing Both Retention and Inversion Pathways in Stereospecific, Nickel-Catalyzed Miyaura Borylations of Allylic Pivalates
  作者：Qi Zhou、Harathi D. Srinivas、Songnan Zhang、Mary P. Watson

  DOI：10.1021/jacs.6b07396

  日期：2016.9.14

  enable access to either enantiomer of allylboronate product from a single enantiomer of readily prepared allylic pivalate substrate. Excellent functional group tolerance, yields, regioselectivities, and stereochemical fidelities are observed. The stereochemical switch from stereoretention to stereoinversion largely depends upon solvent and can be explained by competitive pathways for the oxidative

  我们开发了一种立体有择的、镍催化的烯丙基新戊酸酯的 Miyaura 硼酸化，它提供了高度对映体富集的 α-立体异构 γ-芳基烯丙基硼酸酯，具有良好的产率和区域选择性。我们的互补条件集能够从易于制备的烯丙基新戊酸酯底物的单个对映体中获得烯丙基硼酸酯产物的任一对映体。观察到优异的官能团耐受性、产率、区域选择性和立体化学保真度。从立体保留到立体转化的立体化学转换很大程度上取决于溶剂，可以通过氧化加成步骤的竞争途径来解释。
• 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.