(S)-(-)-2-fluorooctyl aldehyde | 137639-27-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氟化物
• 英文名称: (S)-(-)-2-fluorooctyl aldehyde
• 英文别名: (2S)-fluorooctanal；(S)-2-fluoro-1-octanal；(2S)-2-fluorooctanal
• CAS: 137639-27-1
• 化学式: C₈H₁₅FO
• 分子量: 146.205
• InChiKey: FRXSOKYJGPZJBP-QMMMGPOBSA-N

物化性质

• 沸点：
  166.5±15.0 °C(Predicted)
• 密度：
  0.892±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  10
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-(-)-2-fluorooctyl aldehyde 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 生成 (S)-2-氟辛烷-1-醇
  参考文献：
  名称：

  A General Organocatalyst for Direct α-Functionalization of Aldehydes:  Stereoselective C−C, C−N, C−F, C−Br, and C−S Bond-Forming Reactions. Scope and Mechanistic Insights

  摘要：

  The development of a general organocatalyst for the alpha-functionalization of aldehydes, via an enamine intermediate, is presented. Based on optically active alpha,alpha-diarylprolinol silyl ethers, the scope and applications of this catalyst for the stereogenic formation of C-C, C-N, C-F, C-Br, and C-S bonds are outlined. The reactions all proceed in good to high yields and with excellent enantioselectivities. Furthermore, we will present mechanistic insight into the reaction course applying nonlinear effect studies, kinetic resolution, and computational investigations leading to an understanding of the properties of the alpha,alpha-diarylprolinol silyl ether catalysts.

  DOI：

  10.1021/ja056120u
• 作为产物：
  描述：

  正辛醛 在 S-α,α-双(3,5-二三氟甲基苯基)脯氨醇三甲基硅醚 、 N-氟代双苯磺酰胺 作用下， 以 甲基叔丁基醚 为溶剂， 反应 24.33h， 生成 (S)-(-)-2-fluorooctyl aldehyde
  参考文献：
  名称：

  对映体富集的抗-α-烯丙基-β-氟胺的非对映选择性合成†

  摘要：

  已经开发了抗-α-烯丙基-β-氟胺的高度非对映选择性的合成，包括醛的对映选择性α-氟化，然后进行非对映选择性的Petasis烯丙基硼烷-曼尼希反应。通常，两步获得的产品收率均良好，drs为97：3–99：1，ee为86-92％。将选择的产物转化为3、5和6元环杂环，后两种结合有外环氟。

  DOI：

  10.1039/c9cc02765c

文献信息

• Diastereoselective Petasis‐Borono‐Mannich Crotylation Reactions of Chiral α‐Heteroatom (F, OBz, OH) Aldehydes: Rapid Access to Valuable Mono and Bicyclic Heterocyclic Scaffolds
  作者：Philip J. Chevis、Chi Bong Eric Chao、Christopher Richardson、Christopher J. T. Hyland、Richmond Lee、Stephen G. Pyne

  DOI：10.1002/chem.202301701

  日期：2023.9.21

  The crotylation reactions of chiral α‐F, α‐OBz and α‐OH aldehydes under Petasis‐borono‐Mannich conditions using (E)‐ or (Z)‐crotylboronates and primary amines resulted in γ‐addition products in high dr and high er. α‐F and α‐OBz aldehydes gave 1,2‐anti‐2,3‐syn and 1,2‐anti‐2,3‐anti, products, respectively while an α‐OH aldehyde gave 1,2‐syn‐2,3‐syn products. The stereochemical outcomes of reactions of the former aldehydes can be explained using a six‐membered ring transition state (TS) model in which a Cornforth‐like conformation around the imine intermediate is favoured resulting in 1,2‐anti products. The 2,3‐stereochemical outcome is dependent upon the geometry of the crotylboronate. These TS models were also supported by DFT calculations. The stereochemical outcomes of reactions employing an α‐OH aldehyde can be rationalised as occurring via an open‐TS involving H‐bonding in the imine intermediate between the α‐OH group and the imine N atom. Representative products were converted to highly functionalized 1,2,3,6‐tetrahydropyridines and 3H‐oxazolo[3,4‐a]pyridine‐3‐ones which will be valuable scaffolds in synthesis.

  摘要在Petasis-borono-Mannich条件下，使用(E)-或(Z)-巴豆硼酸酯和伯胺对手性α-F、α-OBz和α-OH醛进行巴豆酰化反应，可得到高dr和高er的γ-加成产物。α-F和α-OBz醛分别生成 1,2-反-2,3-炔和 1,2-反-2,3-反产物，而α-OH醛则生成 1,2-炔-2,3-炔产物。前一种醛反应的立体化学结果可以用一个六元环过渡态（TS）模型来解释，在该模型中，亚胺中间体周围的类似 Cornforth 的构象有利于生成 1,2-反产物。2,3-立体化学结果取决于巴豆硼酸酯的几何形状。这些 TS 模型也得到了 DFT 计算的支持。采用 α-OH 醛的反应的立体化学结果可以合理地认为是通过开放式 TS 发生的，其中涉及 α-OH 基团和亚胺 N 原子之间的亚胺中间体中的 H 键。代表性产物被转化为高度官能化的 1,2,3,6-四氢吡啶和 3H-恶唑并[3,4-a]吡啶-3-酮，它们将成为有价值的合成支架。
• 10.1016/j.tetlet.2024.155179
  作者：Khonde, Nilesh S.、Said, Madhukar S.、Danve, Shivam S.、Kumar, Pradeep

  DOI：10.1016/j.tetlet.2024.155179

  日期：——

  syn/anti-1,3-fluoro amines. The strategy employs α-fluorination catalyzed by proline-derived catalyst, (S)-α,α-bis[3,5-()]-2-pyrrolidinemethanol trimethylsilyl ether followed by Horner−Wadsworth−Emmons (HWE) olefination of aldehydes, and proline-catalyzed α-amination as the key steps. The title compounds showed excellent diastereoselectivity (up to 99:1) and enantioselectivity (up to 99 %).

  开发了一种通用的有机催化方法用于不对称合成α-肼基-γ-氟醇，顺式/反式1,3-氟胺的前体。该策略采用脯氨酸衍生催化剂、(S)-α,α-双[3,5-()]-2-吡咯烷甲醇三甲基硅醚催化的α-氟化，然后进行醛的霍纳-沃兹沃斯-埃蒙斯(HWE)烯化，脯氨酸催化的α-氨基化为关键步骤。标题化合物表现出优异的非对映选择性（高达 99:1）和对映选择性（高达 99%）。
• Direct Asymmetric α-Fluorination of Aldehydes
  作者：Derek D. Steiner、Nobuyuki Mase、Carlos F. Barbas

  DOI：10.1002/anie.200500571

  日期：2005.6.13
• Enantioselective Formation of Stereogenic Carbon-Fluorine Centers by a Simple Catalytic Method
  作者：Mauro Marigo、Doris Fielenbach、Alan Braunton、Anne Kjærsgaard、Karl Anker Jørgensen

  DOI：10.1002/anie.200500395

  日期：2005.6.13
• JPH03197438A
  申请人：——

  公开号：JPH03197438A

  公开（公告）日：1991-08-28