(4S,1'R,6'R)-3-[(4',6'-dimethylcyclohex-3'-ene-1'-yl)carbonyl]-4-iso-propyloxazolidin-2-one | 112530-10-6

• 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,1'R,6'R)-3-[(4',6'-dimethylcyclohex-3'-ene-1'-yl)carbonyl]-4-iso-propyloxazolidin-2-one
• 英文别名: (4S)-3-((4'R,5'R)-1',5'-dimethylcyclohexene-4'-carbonyl)-4-(1-methylethyl)-2-oxazolidinone；(4S)-3-[(1R,6R)-4,6-dimethylcyclohex-3-ene-1-carbonyl]-4-propan-2-yl-1,3-oxazolidin-2-one
• CAS: 112530-10-6
• 化学式: C₁₅H₂₃NO₃
• 分子量: 265.353
• InChiKey: BAGWHDYQKUOUFX-JHJVBQTASA-N

物化性质

• 熔点：
  44.5-46.5 °C
• 沸点：
  391.8±31.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-[(4',6'-dimethylcyclohex-3'-ene-1'-yl)carbonyl]-oxazolidin-2-one 在 lithium hydroxide 、 正丁基锂 、 草酰氯 、 双氧水 、 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 16.0h， 生成 (4S,1'R,6'R)-3-[(4',6'-dimethylcyclohex-3'-ene-1'-yl)carbonyl]-4-iso-propyloxazolidin-2-one
  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

• 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
• Crystal Structures– AManifesto for the Superiority of the Valine-Derived 5,5-Diphenyloxazolidinone as an Auxiliary in Enantioselective Organic Synthesis
  作者：Christoph Gaul、Bernd W. Schweizer、Paul Seiler、Dieter Seebach

  DOI：10.1002/1522-2675(200206)85:6<1546::aid-hlca1546>3.0.co;2-2

  日期：2002.6

  The crystal structures of 32 derivatives of 4-isopropyl-5,5-diplienyl-1,3-oxazolidin-2-one (A and 1 - 31) are presented (Fig. 2 and Tables 1-3). In all but four structures, the Me2CH group is in a disposition that mimick a Me3C group (Figs. 3-5). The five-membered ring shows conformations from an envelope form with the Ph2C group out of the plane containing the other four atoms to the twist form with the twofold axis through the C=O group (Fig. 6, and Table 2). In the entire series, the Me2CH and the neighboring trans Ph group are approximately antiperiplanar (average torsion angle 155degrees). The structural features are used to interpret the previously observed reactivity behavior of the diphenyl-oxazolidinone derivatives. The practical advantages of the title compound over classical Evans auxiliaries are outlined (Figs. I and 7 and Scheme 2): high crystallinity of all derivatives, steric protection of the C=O group in the ring, excellent stereoselectivities in reactions of its derivatives, and safe preparation and easy recovery of the auxiliary.
• Evans, David A.; Chapman, Kevin T.; Hung, Deborah Tan, Angewandte Chemie, 1987, vol. 99, # 11, p. 1197 - 1199
  作者：Evans, David A.、Chapman, Kevin T.、Hung, Deborah Tan、Kawaguchi, Alan T.

  DOI：——

  日期：——
• SuperQuat 5,5-dimethyl-4-iso-propyloxazolidin-2-one as a mimic of Evans 4-tert-butyloxazolidin-2-one
  作者：Steven D. Bull、Stephen G. Davies、A. Christopher Garner、Dennis Kruchinin、Min-Suk Key、Paul M. Roberts、Edward D. Savory、Andrew D. Smith、James E. Thomson

  DOI：10.1039/b605244d

  日期：——

  The incorporation of a gem-dimethyl group at the 5-position of a chiral oxazolidinone biases the conformation of the adjacent C(4)-stereodirecting group such that the gem-dimethyl-4-iso-propyl combination mimics a C(4)-tert-butyl group, providing higher levels of stereocontrol than a simple 4-iso-propyloxazolidinone. The generality of this principle is demonstrated with applications in stereoselective enolate alkylations, kinetic resolutions, Diels–Alder cycloadditions and Pd-catalysed asymmetric acetalisation reactions.

  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。