(4S)-3-(2-methyl-2-propenoyl)-4-(1-methylethyl)-2-oxazolidinone | 112459-59-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4S)-3-(2-methyl-2-propenoyl)-4-(1-methylethyl)-2-oxazolidinone
• 英文别名: (S)-3-(2'-methylacryloyl)-4-iso-propyloxazolidin-2-one；(4S)-N-Methacryloyl-4-isopropyl-2-oxazolidinone；(S)-4-isopropyl-3-methacryloyloxazolidin-2-one；(4S)-3-(2-methylprop-2-enoyl)-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 112459-59-3
• 化学式: C₁₀H₁₅NO₃
• 分子量: 197.234
• InChiKey: JAEVJHCFWZZIKL-MRVPVSSYSA-N

物化性质

• 熔点：
  66.0-67.0 °C(Solv: hexane (110-54-3))
• 沸点：
  256.8±23.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲醇 、 (4S)-3-(2-methyl-2-propenoyl)-4-(1-methylethyl)-2-oxazolidinone 在 氧气 、 copper(l) chloride 、 palladium dichloride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 96.0h， 以66%的产率得到
  参考文献：
  名称：

  Palladium(II)-catalysed asymmetric acetalization of alkenes

  摘要：

  以 4-叔丁基恶唑烷-2-酮为手性助剂的甲基丙烯酰胺在 PdCl2 催化剂存在下与甲醇反应，生成 95% 非对映异构过量的相应缩醛，去除助剂后形成手性缩醛。

  DOI：

  10.1039/c39930000117
• 作为产物：
  描述：

  (S)-4-异丙基-2-唑烷酮 、 甲基丙烯酰氯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以89%的产率得到(4S)-3-(2-methyl-2-propenoyl)-4-(1-methylethyl)-2-oxazolidinone
  参考文献：
  名称：

  SuperQuat 5,5-dimethyl-4-iso-propyloxazolidin-2-one as a mimic of Evans 4-tert-butyloxazolidin-2-one

  摘要：

  在手性噁唑啉酮的5位引入一个双甲基基团会使得邻近的C(4)立体导向基团倾向于特定构象，即双甲基-4-异丙基的组合能模拟一个C(4)叔丁基基团，从而实现更高的立体控制水平，优于简单的4-异丙基噁唑啉酮。这一原理的普遍性在立体选择性烯醇化物烷基化、动力学拆分、狄尔斯-阿尔德环加成和钯催化的不对称缩醛化反应中得到了应用验证。

  DOI：

  10.1039/b605244d

文献信息

• Synthesis of Indole Terpenoid Mimics through a Functionality-Tolerated Eu(fod)₃-Catalyzed Conjugate Addition
  作者：Xiaochun Xiong、Deliang Zhang、Jian Li、Yu Sun、Shupeng Zhou、Ming Yang、Huawu Shao、Ang Li

  DOI：10.1002/asia.201403312

  日期：2015.4

  The chemical synthesis of indole terpenoids of structural and biological interests has attracted remarkable attention. Here we report an Eu(fod)3‐catalyzed indole conjugate addition reaction, which tolerates various acid‐sensitive functional groups. A collection of indole terpenoid mimics have been prepared from natural product‐derived α,β‐unsaturated enones on the basis of this reaction. The further

  具有结构和生物学意义的吲哚类萜的化学合成引起了人们的极大关注。在这里我们报告了Eu（fod）3催化的吲哚共轭加成反应，该反应可耐受各种酸敏感的官能团。在此反应的基础上，从天然产物衍生的α，β-不饱和烯酮制备了吲哚类萜模拟物。吲哚加合物进一步转化为更复杂的天然产物样分子也得到了证明。
• Copper-Catalysed Domino Silylative Aldol Reaction Leading to Stereocontrolled Chiral Quaternary Carbons
  作者：Alexandre Welle、Julien Petrignet、Bernard Tinant、Johan Wouters、Olivier Riant

  DOI：10.1002/chem.201000907

  日期：——

  Asymmetric aldol reaction: A domino silylation–aldol reaction between enoyloxazolidinones and various aldehydes has been developed (see scheme). The process catalysed by a copper complex in the presence of a borosilane led to high diastereoselectivities. Yields between 59 and 90 % and d.r. values between 78:22 to 95:5 were obtained. When methacryloyloxazolidinones were used, a controlled chiral quaternary

  不对称的醛醇缩合反应：已开发出烯酰恶唑烷酮与各种醛类之间的多米诺硅烷基化-醛醇缩合反应（参见方案）。在硼硅烷的存在下由铜络合物催化的过程导致高非对映选择性。获得了59％至90％之间的产率和dr值在78∶22至95∶5之间的值。当使用甲基丙烯酰基恶唑烷酮时，产生了受控的手性季碳。BPin = 4,4,5,5-四甲基-1,3,2-二氧杂硼硼烷-2-基。
• Total Synthesis of the Macrocyclic <i>N</i>-Methyl Enamides Palmyrolide A and 2<i>S</i>-Sanctolide A
  作者：Andrew D. Wadsworth、Daniel P. Furkert、Margaret A. Brimble

  DOI：10.1021/jo502238r

  日期：2014.11.21

  details of the total syntheses of the initially reported and revised structures of the neuroprotective agent palmyrolide A are reported. The key macrocyclization step was achieved using a sequential ring-closing metathesis/olefin isomerization reaction. Furthermore, the total synthesis of the related macrolide (2S)-sanctolide A is reported. The synthesis used key elements from the synthesis of palmyrolide

  报道了神经保护剂棕榈酰吡咯烷酮A的最初报道和修改的结构的全部合成的全部细节。关键的大环化步骤是使用顺序的闭环复分解/烯烃异构化反应实现的。此外，已经报道了相关的大环内酯（2S）-三萜内酯A的全合成。合成过程中使用了棕榈油酸酯A合成中的关键元素，包括RCM /烯烃异构化序列。本文所述的合成工作用于促进天然产物Sanctolide A的立体化学分配，并证明了该方法在合成大环叔烯酰胺天然产物中的效用。
• Asymmetric Diels-Alder cycloaddition reactions with chiral .alpha.,.beta.-unsaturated N-acyloxazolidinones
  作者：David A. Evans、K. T. Chapman、J. Bisaha

  DOI：10.1021/ja00212a037

  日期：1988.2
• Palladium(II)-catalyzed asymmetric acetalization of alkenes
  作者：Takahiro Hosokawa、Toshio Yamanaka、Motohiro Itotani、Shun-Ichi Murahashi

  DOI：10.1021/jo00124a032

  日期：1995.9

  The terminal olefinic carbon of N-methacryloyl-2-oxazolidinones is smoothly acetalized by alcohols in the presence of PdCl2 catalyst. The use of 4(S)-isopropyl-, phenyl-, and tert-butyl-2-oxazolidinones as the chiral auxiliary resulted in the formation of the corresponding (2'S)-acetals in 61, 80, and 95% de, respectively. Reductive removal of the auxiliary with LiAlH4 followed by deacetalization produced (R)-3-hydroxy-2-methylpropanal. The enantiomer of this compound, derived from 4(R)substituted oxazolidinones, served as a building block for synthesizing a 1 beta-methylcarbapenem precursor in high enantiomeric excess. In the acetalization of 3',3'-dideuteriated methacryloyl-4-isopropyloxaiolidinone with MeOH, one D-atom on the terminal olefinic carbon stereoselectively migrated to the chiral center in the product acetal. On the basis of this 1,2-hydride migration and the conformational preference of the methacryloyl moiety, the reaction pathway and the mechanism of the diastereoselection are discussed.