ethyl (S,E)-2-bromo-3-(2,2-dimethyl-1,3-dioxolan-4-yl)prop-2-enoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (S,E)-2-bromo-3-(2,2-dimethyl-1,3-dioxolan-4-yl)prop-2-enoate
• 英文别名: (S)-ethyl 2-bromo-3-(2,2-dimethyl-1,3-dioxolan-4-yl)acrylate；ethyl (E)-2-bromo-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• 化学式: C₁₀H₁₅BrO₄
• 分子量: 279.131
• InChiKey: XUJDGSYIHXLNHH-QAZRXNLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  氟磺酰基二氟乙酸甲酯 、 ethyl (S,E)-2-bromo-3-(2,2-dimethyl-1,3-dioxolan-4-yl)prop-2-enoate 在 六甲基磷酰三胺 、 copper(l) iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以61%的产率得到(Z)/(E)-ethyl 3-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-trifluoromethyl-2-propenoate
  参考文献：
  名称：

  A one-pot synthesis of (E)-α-bromo-α,β-unsaturated esters and their trifluoromethylation: a general and stereoselective route to (E)-α-trifluoromethyl-α,β-unsaturated esters

  摘要：

  Bromination of a phosphonate anion derived in situ from ethyl bis (2,2 2 -trifluoroethyl)phosphonoacetate 3 followed by the addition of aldehydes produced (E)-alpha -bromo-alpha,beta -unsaturated esters 5 stereo selectively. The treatment of 5 with FSO2CF2CO2Me and CuI in DMF/HMPA provided (E)-alpha -trifluoromethyl-alpha,beta -unsaturated esters 6. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01153-4
• 作为产物：
  描述：

  乙基[二(2,2,2-三氟乙氧基)氧膦基]乙酸 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 以59%的产率得到ethyl (S,E)-2-bromo-3-(2,2-dimethyl-1,3-dioxolan-4-yl)prop-2-enoate
  参考文献：
  名称：

  A one-pot synthesis of (E)-α-bromo-α,β-unsaturated esters and their trifluoromethylation: a general and stereoselective route to (E)-α-trifluoromethyl-α,β-unsaturated esters

  摘要：

  Bromination of a phosphonate anion derived in situ from ethyl bis (2,2 2 -trifluoroethyl)phosphonoacetate 3 followed by the addition of aldehydes produced (E)-alpha -bromo-alpha,beta -unsaturated esters 5 stereo selectively. The treatment of 5 with FSO2CF2CO2Me and CuI in DMF/HMPA provided (E)-alpha -trifluoromethyl-alpha,beta -unsaturated esters 6. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01153-4

文献信息

• Diastereoselective Thia-Claisen Rearrangement of Pyrrolidinone-Derived Ketene<i>N</i>,<i>S</i>-Acetals
  作者：Michael Porter、Adam Ellwood、Anne Mortimer、Derek Tocher

  DOI：10.1055/s-2008-1078030

  日期：2008.8

  Thia-Claisen rearrangements of S-allylic ketene N,S-­acetals were carried out using substrates with an external allylic stereogenic centre. High levels of diastereoselectivity were observed only when a bromine substituent was introduced onto the double bond.

  使用带有外部烯丙基手性中心的底物进行了S-烯丙基烯酮N,S-乙缩醛的Thia-Claisen重排反应，仅当双键上引入溴取代基时，才观察到高水平的非对映选择性。
• Reversal of facial selectivity in a thia-Claisen rearrangement by incorporation of a vinylic bromine substituent
  作者：Adam R. Ellwood、Anne J. Price Mortimer、Jonathan M. Goodman、Michael J. Porter

  DOI：10.1039/c3ob41580e

  日期：——

  Thia-Claisen rearrangements have been carried out using N-benzylpyrrolidine-2-thione and chiral allylic bromides derived from D-mannitol. Introduction of a bromine atom onto the double bond of the allylic bromide reverses the sense of diastereoselectivity in the [3,3]-sigmatropic rearrangement. Density functional theory calculations lead us to rationalise the observed selectivity in terms of a Cíeplak

  使用N-苄基吡咯烷-2-硫酮和衍生自D-甘露糖醇的手性烯丙基溴化物进行了Thia-Claisen重排。将溴原子引入烯丙基溴的双键上可以逆转[3,3]-σ重排中的非对映选择性。密度泛函理论计算使我们根据塞普拉克效应合理化了观察到的选择性。
• Enantioselective syntheses of (R)-pipecolic acid, (2R,3R)-3-hydroxypipecolic acid, β-(+)-conhydrine and (−)-swainsonine using an aziridine derived common chiral synthon
  作者：Subhash P. Chavan、Lalit B. Khairnar、Kailash P. Pawar、Prakash N. Chavan、Sanket A. Kawale

  DOI：10.1039/c5ra06429e

  日期：——

  Concise total syntheses of (R)-pipecolic acid, (R)-ethyl-6-oxopipecolate, (2R,3R)-3-hydroxypipecolic acid and formal syntheses of β-(+)-conhydrine, (−)-lentiginosine, (−)-swainsonine and 1,2-di-epi-swainsonine have been accomplished starting from a common chiral synthon. The present strategy employs regioselective aziridine ring opening, Wittig olefination and RCM as the key chemical transformations

  简明的（R）-哌酸，（R）-乙基-6-氧代哌酸酯，（2 R，3 R）-3-羟基哌酸的总合成以及β-（+）-羟基，（-）-龙胆苷的形式合成，（-）-swainsonine和1,2- di - epi -swainsonine已从常见的手性合成子开始完成。本策略采用区域选择性氮丙啶开环，维蒂希烯化和RCM作为关键化学转化。
• Braun, Norbert A.; Klein, Iris; Spitzner, Dietrich, Liebigs Annalen, 1995, # 12, p. 2165 - 2170
  作者：Braun, Norbert A.、Klein, Iris、Spitzner, Dietrich、Vogler, Bernhard、Braun, Siegmar、et al.

  DOI：——

  日期：——
• A one-pot synthesis of (E)-α-bromo-α,β-unsaturated esters and their trifluoromethylation: a general and stereoselective route to (E)-α-trifluoromethyl-α,β-unsaturated esters
  作者：Feng-Ling Qing、Xingang Zhang

  DOI：10.1016/s0040-4039(01)01153-4

  日期：2001.8

  Bromination of a phosphonate anion derived in situ from ethyl bis (2,2 2 -trifluoroethyl)phosphonoacetate 3 followed by the addition of aldehydes produced (E)-alpha -bromo-alpha,beta -unsaturated esters 5 stereo selectively. The treatment of 5 with FSO2CF2CO2Me and CuI in DMF/HMPA provided (E)-alpha -trifluoromethyl-alpha,beta -unsaturated esters 6. (C) 2001 Elsevier Science Ltd. All rights reserved.