(2R,4S)-2-(benzyloxy)pentan-4-ol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,4S)-2-(benzyloxy)pentan-4-ol
• 英文别名: (2S,4R)-4-phenylmethoxypentan-2-ol
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: ZDGYZKNTFSWSEU-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,4S)-2-(benzyloxy)pentan-4-ol 在 bis(2-methoxyethyl) azodicarboxylate 、 4-二苯基膦苯甲酸 、 水 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以97%的产率得到(2R,4R)-2-(benzyloxy)-4-pentanol
  参考文献：
  名称：

  Mitsunobu Reaction with 4-(Diphenylphosphino)benzoic Acid: A Separation-Friendly Bifunctional Reagent that Serves as Both a Reductant and a Pronucleophile

  摘要：

  4-(Diphenylphosphino)benzoic acid was used for the Mitsunobu reaction as a bifunctional reagent that served as both a reductant and a pronucleophile. When combined with di-2-methoxyethyl azodicarboxylate, inversion of a secondary alcohol stereospecifically occurred to give an ester carrying a phosphine oxide group. The reaction mixture was directly hydrolyzed to give an inverted secondary alcohol in sufficient stereo and chemical purities by the presently developed chromatography-free process in conjunction with basic extraction, drying, and concentration.

  DOI：

  10.1055/s-0032-1318327
• 作为产物：
  描述：

  (2R,4R)-2-(benzyloxy)-4-pentanol 在 bis(2-methoxyethyl) azodicarboxylate 、 4-二苯基膦苯甲酸 、 水 、 sodium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以89%的产率得到(2R,4S)-2-(benzyloxy)pentan-4-ol
  参考文献：
  名称：

  Mitsunobu Reaction with 4-(Diphenylphosphino)benzoic Acid: A Separation-Friendly Bifunctional Reagent that Serves as Both a Reductant and a Pronucleophile

  摘要：

  4-(Diphenylphosphino)benzoic acid was used for the Mitsunobu reaction as a bifunctional reagent that served as both a reductant and a pronucleophile. When combined with di-2-methoxyethyl azodicarboxylate, inversion of a secondary alcohol stereospecifically occurred to give an ester carrying a phosphine oxide group. The reaction mixture was directly hydrolyzed to give an inverted secondary alcohol in sufficient stereo and chemical purities by the presently developed chromatography-free process in conjunction with basic extraction, drying, and concentration.

  DOI：

  10.1055/s-0032-1318327

文献信息

• Intramolecular OH⋅⋅⋅Fluorine Hydrogen Bonding in Saturated, Acyclic Fluorohydrins: The γ-Fluoropropanol Motif
  作者：Bruno Linclau、Florent Peron、Elena Bogdan、Neil Wells、Zhong Wang、Guillaume Compain、Clement Q. Fontenelle、Nicolas Galland、Jean-Yves Le Questel、Jérôme Graton

  DOI：10.1002/chem.201503253

  日期：2015.12.1

  is commonly exercised in compound property optimization. However, the influence of fluorination on hydrogen‐bond (HB) properties of adjacent functional groups, as well as the HB‐accepting capacity of fluorine itself, is still not completely understood. Although the formation of OH⋅⋅⋅F intramolecular HBs (IMHBs) has been established for conformationally restricted fluorohydrins, such interaction in

  氟化通常用于化合物性能优化。然而，氟化对相邻官能团氢键（HB）性质以及氟本身的HB接受能力的影响尚不完全清楚。尽管构象限制的氟代醇可以形成 OH⋅⋅⋅F 分子内 HBs (IMHBs)，但柔性化合物中的这种相互作用仍然存在疑问。与之前的报道相比，本文首次证明了无环饱和 γ-氟代醇中存在 OH⋅⋅⋅F IMHB，甚至对于母体 3-氟丙-1-醇也是如此。相对立体化学对相应的h1 J OH⋅⋅⋅F值具有至关重要的影响，如syn ‐ 和anti- 4-氟戊烷-2-ol (6.6 和 1.9 Hz) 所示。OH⋅⋅⋅F IMHBs 的大小及其对整体分子构象、氟化基序和烷基取代水平的强烈依赖性，通过量子化学计算得到了合理化。对于给定的烷基链，“屏蔽规则”适用于 OH⋅⋅⋅F IMHB 能量。令人惊讶的是，预测的 OH⋅⋅⋅F IMHB 能量仅比相应的 OH⋅⋅⋅OMe 弱一些。这些结果为脂肪醇氟化的影
• Conformer Equilibria in 2,4-Disubstituted Pentane Derivatives
  作者：Reinhard W. Hoffmann、Dirk Stenkamp、Thomas Trieselmann、Richard Göttlich

  DOI：10.1002/(sici)1099-0690(199911)1999:11<2915::aid-ejoc2915>3.0.co;2-r

  日期：1999.11

  only two conformations. Substituents have been varied in order to find those which lead to a strong preference of the conformer equilibrium. Studying 2-substituted 4-methylpentanes 3 and 4-benzyloxypentanes 12, it has been shown that substituent effects on the conformer equilibria are not additive, as would be expected on the grounds of steric effects alone. Rather, interactions between polar groups

  2,4-二取代戊烷是基本上仅采用两种构象的分子。为了找到导致构象异构体平衡的强烈偏好的取代基，已经改变了取代基。研究 2-取代的 4-甲基戊烷 3 和 4-苄氧基戊烷 12，已经表明取代基对构象异构体平衡的影响不是相加的，正如仅基于空间效应所预期的那样。相反，极性基团之间的相互作用加强了构象异构体平衡的偏差。当应用于 2,4-二取代戊烷时，氯或邻苯二甲酰亚胺等取代基将构象异构体平衡移动到 gg 构象异构体一侧，优先级超过 90%。
• Stereoselective Synthesis and Reactions of Secondary Alkyllithium Reagents Functionalized at the 3-Position
  作者：Kohei Moriya、Dorian Didier、Meike Simon、Jeffrey M. Hammann、Guillaume Berionni、Konstantin Karaghiosoff、Hendrik Zipse、Herbert Mayr、Paul Knochel

  DOI：10.1002/anie.201409165

  日期：2015.2.23

  Secondary alkyllithium reagents bearing an OTBS group (TBS=tert‐butyldimethylsilyl) at the 3‐position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3‐difunctionalized derivatives

  可以通过I / Li交换从相应的仲烷基碘化物的非对映异构体混合物中立体聚合制备在3位带有OTBS基团（TBS =叔丁基二甲基甲硅烷基）的仲烷基锂试剂。这些锂试剂可与多种亲电试剂（包括碳亲电试剂）反应，并保留构型，以产生具有良好非对映选择性的各种1,3-双官能化衍生物。动力学研究表明，3-甲硅烷氧基可大大加速锂取代的碳原子上的差向异构。该方法为构建具有出色立体选择性的手性开链分子提供了新途径。
• Enantioselective Ring Cleavage of Dioxane Acetals Mediated by a Chiral Lewis Acid:  Application to Asymmetric Desymmetrization of <i>meso</i>-1,3-Diols
  作者：Toshiro Harada、Kousuke Sekiguchi、Tomohito Nakamura、Jun Suzuki、Akira Oku

  DOI：10.1021/ol0165286

  日期：2001.10.1

  text]. Phenylalanine-derived B-aryl-N-tosyloxazaborolidinones selectively activate one of two enantiotopic oxygen atoms in prochiral anti dioxane acetals derived from meso-1,3-diols, leading to enantioselective formation of ring-cleavage products. The reaction is utilized as a key step in asymmetric desymmetrization of meso-1,3-diols.

  [反应：请参见文字]。苯丙氨酸衍生的B-芳基-N-甲苯磺酰氮杂硼硼烷酮选择性地活化衍生自meso-1,3-二醇的前手性抗二恶烷缩醛中的两个对映体氧原子之一，导致对映选择性形成环裂解产物。该反应被用作meso-1,3-二醇不对称脱对称的关键步骤。
• Mitsunobu Reaction with 4-(Diphenylphosphino)benzoic Acid: A Separation-Friendly Bifunctional Reagent that Serves as Both a Reductant and a Pronucleophile
  作者：Takashi Sugimura、Natsuko Muramoto、Kazuki Yoshino、Tomonori Misaki

  DOI：10.1055/s-0032-1318327

  日期：——

  4-(Diphenylphosphino)benzoic acid was used for the Mitsunobu reaction as a bifunctional reagent that served as both a reductant and a pronucleophile. When combined with di-2-methoxyethyl azodicarboxylate, inversion of a secondary alcohol stereospecifically occurred to give an ester carrying a phosphine oxide group. The reaction mixture was directly hydrolyzed to give an inverted secondary alcohol in sufficient stereo and chemical purities by the presently developed chromatography-free process in conjunction with basic extraction, drying, and concentration.