(S)-4-isopropyl-3-[(E)-2-pentenoyl]-2-oxazolidinone | 186802-05-1

• 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: (S)-4-isopropyl-3-[(E)-2-pentenoyl]-2-oxazolidinone
• 英文别名: (S,E)-4-isopropyl-3-(pent-2-enoyl)oxazolidin-2-one；(4S)-3-[(E)-pent-2-enoyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 186802-05-1
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: XDYSJPXXICNGHW-VUHVRTRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  (S)-4-isopropyl-3-[(E)-2-pentenoyl]-2-oxazolidinone 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 1,2-双(二苯基膦)乙烷 、 lithium hexamethyldisilazane 作用下， 以 甲苯 为溶剂， 反应 2.5h， 生成 dimethyl 2-[(E,2R)-5-oxo-5-[(4S)-2-oxo-4-propan-2-yl-1,3-oxazolidin-3-yl]pent-3-en-2-yl]propanedioate
  参考文献：
  名称：

  基于手性二烯酸酯的远程不对称诱导：不对称的α-氧化/ Pd（0）催化的烯丙基取代序列导致γ-手性的α，β-不饱和酸衍生物

  摘要：

  衍生自手性α，β-或β，γ-不饱和酰亚胺的二烯酸酯与二苄基过氧二碳酸酯的不对称α-氧基化反应，随后是生成的烯丙基碳酸酯与各种亲核试剂的Pd（0）催化反应（烷基化，醚化和胺化） ）显示出）分别为γ-（S）-或-（R）-构型的α，β-不饱和酰亚胺提供了高水平的立体控制。

  DOI：

  10.1016/s0040-4039(98)00770-9
• 作为产物：
  描述：

  反式-2-戊烯酸 在 正丁基锂 、 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (S)-4-isopropyl-3-[(E)-2-pentenoyl]-2-oxazolidinone
  参考文献：
  名称：

  吡咯并可见光催化不对称合成[1,2一]吲哚通过分子间[3 + 2]环加成†

  摘要：

  吡咯并[1,2- a ]吲哚的分子间非对映选择性和对映选择性合成是通过甲硅烷基吲哚衍生物与α，β-不饱和N-酰基恶唑烷酮通过光催化和路易斯酸催化的[3 + 2]环加成反应而开发的。

  DOI：

  10.1039/c9cc05838a

文献信息

• Diastereoselective Conjugate Addition of Cyanide to α,β-Unsaturated ­Oxazolidinones: Enantioselective Synthesis of <i>ent</i>-Pregabalin and Baclofen
  作者：Alan Armstrong、Nicola Convine、Matthew Popkin

  DOI：10.1055/s-2006-941584

  日期：2006.6

  Conjugate addition of cyanide to chiral α,β-unsaturated oxazolidinones catalyzed by samarium(III) isopropoxide proceeds with good diastereoselectivity. The addition products can be ­converted into the biologically active targets ent-pregabalin and ­baclofen.

  手性α,β-不饱和恶唑啉酮的氰基共轭加成反应在钐(III)异丙氧化物催化下进行，具有良好的非对映选择性。加成产物可转化为生物活性目标药物ent-普瑞巴林和巴氯芬。
• Chiral dienolate chemistry in remote asymmetric induction: the allylation / cope rearrangement sequence leading to γ-chiral α, β-unsaturated acid derivatives
  作者：Katsuhiko Tomooka、Atsushi Nagasawa、Shih-Yi Wei、Takeshi Nakai

  DOI：10.1016/s0040-4039(96)02077-1

  日期：1996.12

  allylation of the dienolate derived from the chiral α, β- or β, γ-unsaturated imidefollowed by the Cope rearrangement is shown to effect the net remote asymmetric induction to create a new chirality of either configuration at the γ-position in high % de. The utility of this approach is shown in the asymmetric synthesis of the C6 side chain of Zaragozic acid A.

  由Cope重排引起的手性α，β或β，γ-不饱和imidefolol衍生的二烯酸酯的烯丙基化显示出有效的远程不对称诱导作用，从而在高％de时在γ位置产生了任一构型的新手性。Zaragozic acid A的C6侧链的不对称合成显示了该方法的实用性。
• Double Stereocontrol in α-Alkylation of Chiral Lithium Dienolates Generated from (E)-α,β-Olefinic Amides and Esters
  作者：Katsuhiko Tomooka、Atsushi Nagasawa、Takeshi Nakai

  DOI：10.1246/cl.1998.1049

  日期：1998.10

  The methylation of the lithium dienolate generated from (E)-α,β-olefinic amide with Katsuki’s chiral auxiliary affords the α-methylated β,γ-enamide in an exceptionally high Z-selectivity (99%) over the terminal olefinic bond along with 99% de at the α-chiral center. The origin of the high Z-selectivity is discussed.

  用 Katsuki 的手性助剂对 (E)-α,β-烯烃酰胺生成的二烯酸锂进行甲基化，可得到α-甲基化的 β,γ-烯酰胺，在末端烯烃键上具有极高的 Z 选择性（99%），同时在 α-手性中心具有 99% 的 de。本文讨论了高 Z 选择性的来源。
• Enantioselective Construction of Cyclic Ethers by An Aldol-Cyclization Sequence
  作者：Paul Galatsis、Scott D. Millan、George Ferguson

  DOI：10.1021/jo961904z

  日期：1997.7.1

  We have modified the substrate used in deconjugative aldol-cyclizations by incorporating the Evans chiral auxiliary. The deconjugative aldol step, using boron enolates, gave the expected products with complete syn-aldol stereochemistry. These compounds could then undergo an iodine-mediated cyclization to form optically active products. Oxetanes and fused ring tetrahydrofurans were easily assembled with a variety of substitution patterns and with excellent enantiocontrol. The deconjugation of acyclic chiral enimides resulted in the loss of control of olefin geometry. However, these compounds did appear to cyclize with excellent enantiocontrol.
• Diastereoselective Synthesis of Tetrahydrofurans by Lewis Acid Catalyzed Intermolecular Carbenoid–Carbonyl Reaction–Cycloaddition Sequences: Unusual Diastereoselectivity of Lewis Acid Catalyzed Cycloadditions
  作者：Yuta Hashimoto、Kennosuke Itoh、Akikazu Kakehi、Motoo Shiro、Hiroyuki Suga

  DOI：10.1021/jo400858u

  日期：2013.6.21

  The effects of including metal salts for three. component reactions involving alpha-alkyl-alpha-diazo esters, aromatic aldehydes, and 3-(2-alkenoyl)-2-oxazolidinones are described, in terms of yields and diastereoselectivities. Metal tetrafluorborates (10-30 mol %) such as Co(BF4)(2)center dot 6H(2)O, Ni(BF4)(2)center dot 6H(2)O, and AgBF4 were effective in delivering high yields and diastereoselectivities (93:7 to 99:1) of the corresponding tetrahydrofuran derivatives while suppressing the competitive formation of 1,3-dioxolane. Using (S)-3-(2-alkenoyl)-4-isopropyl-2-oxazolidinones as the dipolarophiles in the three-component reactions, in the presence of Ni(BF4)(2)center dot 6H(2)O or Co(ClO4)(2)center dot 6H(2)O (10-30 mol %), optically active tetrahydrofurans that possess four successive asymmetric centers were synthesized in high diastereoselectivities (99:1). On the basis of the configuration of the cycloadduct using the X-ray analysis, the high diastereoselectivity could be explained by the unusual Re-face approach to the dipolarophile in the presence of the Lewis acid, proceeding through the s-cis conformer of the 3-(2-alkenoyl)-2-oxazolidinone with the two carbonyls in opposing directions (dipole-dipole interaction).