trans-3-(4-chlorophenyl)-N,N-diethyloxirane-2-carboxamide

• 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: trans-3-(4-chlorophenyl)-N,N-diethyloxirane-2-carboxamide
• 英文别名: (2S,3R)-3-(4-chlorophenyl)-N,N-diethyloxirane-2-carboxamide
• 化学式: C₁₃H₁₆ClNO₂
• 分子量: 253.729
• InChiKey: LXSJBDJZWKFLHW-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  32.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N,N-二乙基-2-溴乙酰胺 在 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 48.08h， 生成 trans-3-(4-chlorophenyl)-N,N-diethyloxirane-2-carboxamide
  参考文献：
  名称：

  用于缩水甘油酰胺非对映选择性合成的叶立德铵。

  摘要：

  开发了一种用于合成缩水甘油酰胺的高度反式选择性方案。该方法通过使带有α-羰基的稳定铵叶立德与芳香醛反应，以中等至良好的收率获得环氧乙烷。

  DOI：

  10.1039/c0cc04821f

文献信息

• Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions
  作者：Johanna Novacek、Lukas Roiser、Katharina Zielke、Raphaël Robiette、Mario Waser

  DOI：10.1002/chem.201602052

  日期：2016.8.1

  carbonyl‐stabilised ammonium ylide‐mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine‐based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.

  通过实验和计算手段系统地研究了羰基稳定的铵叶立德介导的环氧化反应的关键因素，由此获得的能量分布为观察到的实验结果提供了解释。此外，我们还能够鉴定出第一个基于叔胺的手性助剂，该助剂可实现高对映选择性和高产率，用于此类环氧化反应。
• Identification of the best-suited leaving group for the diastereoselective synthesis of glycidic amides from stabilised ammonium ylides and aldehydes
  作者：Richard Herchl、Martin Stiftinger、Mario Waser

  DOI：10.1039/c1ob05721a

  日期：——

  In comparison to the use of sulfur ylides, the use of ammonium ylides for the synthesis of epoxides is significantly less developed. As a part of our systematic investigations concerning the use of amide-stabilised ammonium ylides for the synthesis of glycidic amides we have focused on the identification of the best-suited amino leaving group for this purpose. Whereas tertiary amines like quinuclidine

  与使用硫叶立德相比，使用铵叶立德合成环氧化物的情况明显较少。作为我们关于使用酰胺稳定的叶立德铵合成缩水甘油酰胺的系统研究的一部分，我们专注于为此目的鉴定最适合的氨基离去基团。而叔胺如奎宁环 或金鸡纳生物碱被发现不适合形成环氧化物， 三甲胺被发现是选择的离去基团，以 > 90% 的优异产率产生反式缩水甘油酰胺。
• Asymmetric synthesis of (2R,3S )-2,3-epoxyamides via camphor-derived sulfonium ylides
  作者：Yong-Gui Zhou、Xue-Long Hou、Li-Xin Dai、Li-Jun Xia、Ming-Hua Tang

  DOI：10.1039/a806189k

  日期：——

  Enantiomerically enriched trans-2,3-epoxyamides 3 were prepared by the reaction of aldehydes 2 with camphor-derived chiral sulfonium ylide 1 in good yields and moderate to good ee values. The absolute configuration of the reaction product is also determined by chemical transformations.

  通过醛2与樟脑衍生的手性sulf叶立德1的反应，可以以良好的收率和中等至良好的ee值制备对映体富集的反式-2,3-环氧酰胺3。反应产物的绝对构型也通过化学转化来确定。
• [EN] ASYMMETRIC SYNTHESIS OF GLYCIDIC AMIDES<br/>[FR] SYNTHESE ASYMETRIQUE D'AMIDES GLYCIDIQUES
  申请人：UNIV BRISTOL

  公开号：WO2003087075A1

  公开（公告）日：2003-10-23

  Enantiomerically enriched trans-2,3-epoxyamides of the formula (I) in which R1 is a 1-18C aliphatic hydrocarbyl optionally substituted by one or more substituent groups selected from halo, nitro, phenyl and -ORW, where RW is H, 1-6C alkyl, benzyl or phenyl, or is aryl containing from 6-12 ring carbon atoms which is optionally substituted by one or more substituent groups selected from 1-6C alkyl, halo, nitro, phenyl, benzyl and -ORW, where RW is as defined above, or is a monocyclic or fused bicyclic heterocyclic group containing at least one heteroatom selected from N, O and S which group is optionally substituted by one or more substituent groups selected from 1-6C alkyl, halo, nitro, phenyl, benzyl and -ORW, where RW is as defined above; R2 and R3 are the same or different group selected from H, 1-6C alkyl optionally substituted with one or more substituent groups selected from halo, nitro, phenyl and -ORW, where RW is as defined above, 2-6C alkenyl optionally substituted with one or more substituent groups selected from halo, nitro, phenyl and -ORW, where RW is as defined above, phenyl optionally substituted by one or more substituent groups selected from 1-6C alkyl, halo, nitro, phenyl, benzyl and -ORW, where RW is as defined above, and monocyclic heterocyclic groups containing one or more heteroatoms selected from O, S and N, optionally substituted with one or more substituent groups selected from 1-6C alkyl, halo, nitro, phenyl, benzyl and -ORW, where RW is as defined above or R2 or R3, or R2 or R3, together with the nitrogen atom to which they are attached, form a heterocyclic ring, are made by a method comprising reacting a sulfonium salt of the formula (II) wherein R2 and R3 are as defined above, R4 is a group selected from 1-12C alkyl, 6-12C aryl and 7-13C aralkyl and -SiMe3, R5 is 1-4C alkyl group and X- is a counterion, with an aldehyde of the formula R1CHO, where R1 is as defined above, in a solvent in the presence of a base. The use of this method gives excellent yields of the trans epoxides. Sulfonium salts of the formula (II), as defined above, are also disclosed.

  公式（I）中的对映体富集的trans-2,3-环氧酰胺，其中R1是1-18C脂肪烃基，可选地被一个或多个取代基所取代，所选的取代基包括卤素，硝基，苯基和-ORW，其中RW为H，1-6C烷基，苄基或苯基，或是含有6-12个环碳原子的芳基，可选地被一个或多个取代基所取代，所选的取代基包括1-6C烷基，卤素，硝基，苯基，苄基和-ORW，其中RW如上所定义，或是含有至少一个异原子（N，O和S）的单环或融合双环杂环基团，可选地被一个或多个取代基所取代，所选的取代基包括1-6C烷基，卤素，硝基，苯基，苄基和-ORW，其中RW如上所定义；R2和R3是相同或不同的基团，所选的基团包括H，1-6C烷基，可选地被一个或多个取代基所取代，所选的取代基包括卤素，硝基，苯基和-ORW，其中RW如上所定义，2-6C烯基，可选地被一个或多个取代基所取代，所选的取代基包括卤素，硝基，苯基和-ORW，其中RW如上所定义，苯基，可选地被一个或多个取代基所取代，所选的取代基包括1-6C烷基，卤素，硝基，苯基，苄基和-ORW，其中RW如上所定义，以及含有一个或多个异原子（O，S和N）的单环杂环基团，可选地被一个或多个取代基所取代，所选的取代基包括1-6C烷基，卤素，硝基，苯基，苄基和-ORW，其中RW如上所定义，或R2或R3，或R2或R3与它们连接的氮原子一起形成一个杂环环；通过在碱存在下，在溶剂中反应公式（II）的磺鎵盐，其中R2和R3如上所定义，R4是所选的基团，包括1-12C烷基，6-12C芳基和7-13C芳基烷基和-SiMe3，R5是1-4C烷基，X-是一个计数离子，与公式R1CHO的醛在溶剂中反应来制备这些化合物。使用此方法可获得优异的trans环氧化物收率。公式（II）中的磺鎵盐也被揭示。
• Catalytic sulfur ylide reactions: Use of diazoacetamides for the diastereoselective synthesis of glycidic amides
  作者：Varinder K. Aggarwal、Paul Blackburn、Robin Fieldhouse、Ray V.H. Jones

  DOI：10.1016/s0040-4039(98)01852-8

  日期：1998.11

  Diazoacetamides react with aldehydes in the presence of catalytic quantities of Cu(acac)(2) (5 mol%) and tetrahydrothiophene (20 mol%) to give glycidic amides in good yields and high diastereoselectivity. (C) 1998 Elsevier Science Ltd. All rights reserved.