(4S)-3-(2-methyl-2-propenoyl)-4-phenyl-2-oxazolidinone | 154499-36-2

• 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-phenyl-2-oxazolidinone
• 英文别名: (4S)-4-phenyl-N-methacryloyloxazolidin-2-one；(4S)-N-Methacryloyl-4-phenyl-2-oxazolidinone；(S)-3-methacryloyl-4-phenyloxazolidin-2-one；3-Methacryloyl-4beta-phenyloxazolidine-2-one；(4S)-3-(2-methylprop-2-enoyl)-4-phenyl-1,3-oxazolidin-2-one
• CAS: 154499-36-2
• 化学式: C₁₃H₁₃NO₃
• 分子量: 231.251
• InChiKey: UJBHHSVLIFXDJH-LLVKDONJSA-N

物化性质

• 沸点：
  343.0±45.0 °C(Predicted)
• 密度：
  1.212±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  (4S)-3-(2-methyl-2-propenoyl)-4-phenyl-2-oxazolidinone 、 烯丙基三甲基硅烷 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以88%的产率得到(4S)-3-((2R)-methyl-5-hexenoyl)-4-phenyl-2-oxazolidinone
  参考文献：
  名称：

  Conjugate addition of allylsilanes to α,β-unsaturated N-acyloxazolidinones

  摘要：

  The conjugate addition of allyltrimethylsilane to alpha,beta-unsaturated N-acyloxazolidinone at -78 degrees C in the presence of TiCl4 gave the allylation product 3. However, when the reaction was carded out at room temperature, a small amount of cyclopentane adduct 4 was observed. The cyclopentane product formation can be prevented by employing BF3.OEt(2) as a Lewis acid. The enantioselective synthesis of optically pure 3-substituted-5-hexenoic acids was achieved by employing chiral oxazolidinone as a chiral auxiliary.

  DOI：

  10.1016/s0040-4020(01)80818-8
• 作为产物：
  描述：

  (S)-4-苯基-2-恶唑烷酮 、 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， 以94%的产率得到(4S)-3-(2-methyl-2-propenoyl)-4-phenyl-2-oxazolidinone
  参考文献：
  名称：

  Palladium(II)-catalyzed asymmetric acetalization of alkenes

  摘要：

  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.

  DOI：

  10.1021/jo00124a032

文献信息

• 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 conjugate addition of thiols to chiral methacryloyloxazolidinones
  作者：Tsung-Chin Tseng、Ming-Jing Wu

  DOI：10.1016/0957-4166(95)00208-7

  日期：1995.7

  The conjugate addition of thioacetic acid (3 equivalents) to (4S)-4-phenyl-N-methacryloyloxazolidin-2-one (3) in the presence of TiCl4 (1.5 equivalents) gave the addition adducts in 87% yield and only 14% de. When this reaction was carried out in the absence of TiCl4, good diastereoselectivity (94% de) was observed. A similar result was obtained by employing thiobenzoic acid as a nucleophile. The reaction of 3 with other thiols, such as thiophenol, 4-methoxythiophenol, 2-methoxytbiophenol, methyl 3-mercatopropionate, methyl thioglycolate and methyl thiosalicylate, required TiCl4 (1.5 equivalents) to give the addition adducts in good chemical yields and the diastereoselectivities are ranging from 50 to 82% de. 2-Aminothiophenol was also employed in this study to give the addition adducts in 60% yield and 70% de when the reaction was carried out in the absence of TiCl4. In the presence of TiCl4, this reaction provided the addition adducts as racemic mixture in 28% yield along with 1,5-benzothiazepin-4-one 10 in 56% yield.
• Wu, Ming-Jung; Yeh, Jiann-Yih, Organic Preparations and Procedures International, 1994, vol. 26, # 6, p. 671 - 674
  作者：Wu, Ming-Jung、Yeh, Jiann-Yih

  DOI：——

  日期：——
• 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.