(+/-)-cis-2,3-epoxynonane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (+/-)-cis-2,3-epoxynonane
• 英文别名: rac-(2R,3S)-2-hexyl-3-methyloxirane；rac-cis-2-hexyl-3-methyloxirane；(2S,3R)-2-hexyl-3-methyloxirane
• 化学式: C₉H₁₈O
• 分子量: 142.241
• InChiKey: IKYJCWFNSKISSG-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-cis-2,3-epoxynonane 在 一氧化碳 、 C₃₈H₅₆AlN₂O₆⁽¹⁺⁾*C₅MnO₅^(1-) 作用下， 以 四氢呋喃 为溶剂， 80.0 ℃ 、8.27 MPa 条件下， 反应 5.0h， 以78%的产率得到2-壬烯
  参考文献：
  名称：

  具有立体化学反转的 2,3-二取代环氧化物的羰基化催化脱氧：另一种烯烃异构化方法

  摘要：

  促进烯烃立体化学反转的反应是现代有机合成领域罕见的、广受欢迎的转化。尽管存在许多异构化反应，但大多数方法需要特定的、高度活化的底物来实现可观的转化，而不会形成副产物。在立体转化环氧化物羰基化反应的推动下，我们开发了一个两步环氧化/脱氧过程，导致烯烃立体化学的整体转化。与大多数脱氧系统不同，考虑到生成的二氧化碳副产物的气态性质，一氧化碳被用作终端还原剂，防止了困难的反应后分离。各种烷基取代的顺式和反式环氧化物可以分别还原为反式和顺式烯烃，立体定向性 > 99:1，产率高达 95%，

  DOI：

  10.1021/jacs.0c02653
• 作为产物：
  描述：

  顺式-2-壬烯 在 双氧水 作用下， 反应 5.0h， 生成 (+/-)-cis-2,3-epoxynonane
  参考文献：
  名称：

  Chloroperoxidase-catalyzed asymmetric oxidations: substrate specificity and mechanistic study.

  摘要：

  The substrate specificity of chloroperoxidase from Caldaromyces fumago in a number of halide-independent reactions was investigated and the ability of this enzyme to perform benzylic hydroxylations with high enantioselectivity is revealed. The substrate repertoire of chloroperoxidase is expanded and the enantioselectivity data for synthetically useful epoxidations are reported. The enzyme epoxidizes straight chain aliphatic and cyclic cis-olefins in a highly stereoselective manner favoring small unsubstituted substrates in which the double bond is not more than two carbon atoms from the terminal. The epoxidation of short-chain prochiral terminal dienes proceeds with high diastereoselectivity and moderate enantioselectivity, yielding monoepoxides exclusively. Unsubstituted straight-chain terminal olefins seven carbons or longer are epoxidized poorly. Aliphatic and aromatic alcohols are efficiently oxidized to aldehydes and acids. The utilization of radical probe substrate trans-2-phenyl-1-methylcyclopropane revealed that the mechanism of chloroperoxidase-catalyzed hydroxylation is incompatible with the existence of a discrete radical intermediate and most likely proceeds via transfer of the oxygen atom from the high valent iron oxo intermediate directly to the substrate.

  DOI：

  10.1021/ja00147a001

文献信息

• Enantioselective Epoxidation of Nonconjugated <i>cis</i>-Olefins by Chiral Dioxirane
  作者：Christopher P. Burke、Yian Shi

  DOI：10.1021/ol901724v

  日期：2009.11.19

  A variety of nonconjugated cis-olefins has been enantioselectively epoxidized with chiral ketones 2, and up to 92% ee has been obtained. The two prochiral faces of an olefin are likely stereodifferentiated by the relative hydrophobicity of the olefin substituents and/or allylic oxygen functionality.

  多种非共轭顺式烯烃已与手性酮2对映选择性环氧化，获得了高达 92% 的 ee。烯烃的两个前手性面可能因烯烃取代基和/或烯丙基氧官能团的相对疏水性而立体分化。
• Titanium-Catalyzed Asymmetric Epoxidation of Non-Activated Olefins with Hydrogen Peroxide
  作者：Yuji Sawada、Kazuhiro Matsumoto、Tsutomu Katsuki

  DOI：10.1002/anie.200700949

  日期：2007.6.11
• Carbonylation of <i>cis</i>-Disubstituted Epoxides to <i>trans</i>-β-Lactones: Catalysts Displaying Steric and Contrasteric Regioselectivity
  作者：Michael Mulzer、Geoffrey W. Coates

  DOI：10.1021/jo501899e

  日期：2014.12.19

  trans-beta-Lactones are a versatile and useful class of compounds, but reliable methods for their direct synthesis are still limited. Addressing this problem, we present herein two catalysts for the regioselective carbonylation of cis-disubstituted epoxides. The two catalysts show high activities and opposing regioselectivities so that either one of the two possible beta-lactone regioisomers can be obtained selectively.
• A kinetic resolution of racemic epoxides by a chiral lithium amide
  作者：Masatoshi Asami、Noriko Kanemaki

  DOI：10.1016/s0040-4039(01)93729-3

  日期：1989.1
• Carbonylative, Catalytic Deoxygenation of 2,3-Disubstituted Epoxides with Inversion of Stereochemistry: An Alternative Alkene Isomerization Method
  作者：Jessica R. Lamb、Aran K. Hubbell、Samantha N. MacMillan、Geoffrey W. Coates

  DOI：10.1021/jacs.0c02653

  日期：2020.4.29

  activated substrates to achieve appreciable conversion without side product formation. Motivated by stereoinvertive epoxide carbonylation reactions, we developed a two-step epoxidation/deoxygenation process that results in overall inversion of alkene stereochemistry. Unlike most deoxygenation systems, carbon monoxide was used as the terminal reductant, preventing difficult postreaction separations, given

  促进烯烃立体化学反转的反应是现代有机合成领域罕见的、广受欢迎的转化。尽管存在许多异构化反应，但大多数方法需要特定的、高度活化的底物来实现可观的转化，而不会形成副产物。在立体转化环氧化物羰基化反应的推动下，我们开发了一个两步环氧化/脱氧过程，导致烯烃立体化学的整体转化。与大多数脱氧系统不同，考虑到生成的二氧化碳副产物的气态性质，一氧化碳被用作终端还原剂，防止了困难的反应后分离。各种烷基取代的顺式和反式环氧化物可以分别还原为反式和顺式烯烃，立体定向性 > 99:1，产率高达 95%，