(4R)-3-allenyl-4-(diphenylmethyl)oxazolidin-2-one | 256382-53-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4R)-3-allenyl-4-(diphenylmethyl)oxazolidin-2-one
• 英文别名: 2-Oxazolidinone, 4-(diphenylmethyl)-3-(1,2-propadienyl)-, (4R)-
• CAS: 256382-53-3
• 化学式: C₁₉H₁₇NO₂
• 分子量: 291.349
• InChiKey: VYMLNEVDRQOXOQ-KRWDZBQOSA-N

物化性质

• 沸点：
  412.6±38.0 °C(Predicted)
• 密度：
  1.186±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4R)-3-allenyl-4-(diphenylmethyl)oxazolidin-2-one 在 六甲基磷酰三胺 、 正丁基锂 、 四氯化锡 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 19.92h， 生成 (R)-4-benzhydryl-3-((1S,4S,5S)-5-(4-((tert-butyldimethylsilyl)oxy)butanoyl)bicyclo[2.2.2]oct-2-en-2-yl)oxazolidin-2-one
  参考文献：
  名称：

  A Highly Stereoselective Diels–Alder Cycloaddition of Enones with Chiral Cyclic 2-Amidodienes Derived from Allenamides

  摘要：

  Lewis acid promoted Diels-Alder cycloadditions of a series of de novo chiral cyclic 2-amidodienes are described. These cyclic 2-amidodienes are derived from chiral alpha-allyl allenamides via a sequence of E-selective 1,3-H shift and 6 pi-electron pericyclic ring closure. With enones serving as effective dienophiles, these cycloadditions can be highly diastereoselective depending upon the chiral amide substituent, thereby representing a facile entry to optically enriched [2.2.2]bicyclic manifolds.

  DOI：

  10.1021/ol402254p
• 作为产物：
  描述：

  (R)-(+)-4-(二苯基甲基)-2-恶唑烷酮 在 potassium tert-butylate 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 32.0h， 生成 (4R)-3-allenyl-4-(diphenylmethyl)oxazolidin-2-one
  参考文献：
  名称：

  (4R)-3-Allenyl-4-(diphenylmethyl)oxazolidin-2-one, an unsubstituted allenamide

  摘要：

  The first X-ray structure of an unsubstituted allenamide, C19H17NO2, is reported. The solid-state phase supports the notion that a key minimum conformation of allenamides can be invoked to rationalize the observed stereochemical outcomes in many of our methodological studies employing allenamides. This minimum conformation involves two important factors, i.e. having approximate coplanarity between the planes of the oxazolidinone ring and the internal olefin, and having the allene moiety facing away from the carbamate carbonyl group. The C-N-C=C torsion angle that quantifies this approximate coplanarity between the plane of the oxazolidinone ring and that of the internal olefin, as determined from this crystallographic study, is. 19.1 (2)degrees. A minimized structural calculation, which determined this angle to be -16.1degrees, is in close agreement. Additional structural features include a probable pi-pi interaction between the allene moiety and a benzene ring, and non-classical hydrogen bonding in the form of weak C-H...O interactions that are responsible for the formation of two-dimensional networks.

  DOI：

  10.1107/s0108270104023121

文献信息

• Efficient preparations of novel ynamides and allenamides
  作者：Lin-Li Wei、Jason A. Mulder、Hui Xiong、Craig A. Zificsak、Christopher J. Douglas、Richard P. Hsung

  DOI：10.1016/s0040-4020(00)01014-0

  日期：2001.1

  achiral allenamides, ynamides are prepared from enamides via bromination followed by base-induced elimination of the Z-bromoenamides. These ynamides and allenamides possess improved thermal stability compared to ynamines and allenamines. They can be isolated, purified, and handled with ease, and thus, should be synthetically more useful than traditional ynamines and allenamines.

  在此描述了一系列新型的酰胺和烯丙酰胺的实用合成。尽管炔丙基酰胺的碱诱导的异构化方案导致一系列手性和非手性烯丙酰胺，但是通过溴化由酰胺制备炔基酰胺，然后进行碱诱导的Z-溴烯酰胺的消除。与炔胺和烯丙胺相比，这些炔酰胺和烯丙酰胺具有改进的热稳定性。它们可以轻松分离，纯化和处理，因此在合成上应比传统的ynamines和allenamines更有用。
• An Unexpected Reversal of Diastereoselectivity in the [4+3]-Cycloaddition Reaction of Nitrogen-Stabilized Oxyallyl Cations with Methyl 2-Furoate
  作者：Richard Hsung、Jennifer Antoline

  DOI：10.1055/s-2008-1042765

  日期：——

  An unexpected reversal of diastereoselectivity in the [4+3] cycloaddition of methyl 2-fuorate with nitrogen-stabilized oxyallyl cations derived from epoxidation of chiral allenamides is described here. This intriguing reversal in favor of the endo-II cycloaddition pathway is likely a result of minimizing the dipole interaction between the oxyallyl cation and ester carbonyl of methyl 2-fuorate.

  这里描述了在 2-氟酸甲酯与氮稳定的氧烯丙基阳离子的 [4+3] 环加成反应中非对映选择性的意外逆转，该阳离子源自手性烯丙酰胺的环氧化。这种有利于内-II 环加成途径的有趣逆转可能是最小化氧烯丙基阳离子与 2​​-氟甲酸甲酯的酯羰基之间偶极相互作用的结果。
• Facile Synthesis of 3-Amido-Dienynes via a Tandem α-Propargylation–Isomerization of Chiral Allenamides and their Applications in Diels–Alder Cycloadditions
  作者：Zhi-Xiong Ma、Li-Chao Fang、Bryan Haugen、Daniel Bruckbauer、John Feltenberger、Richard Hsung

  DOI：10.1055/s-0036-1590899

  日期：2017.12

  A series of de novo 3-amido-dienynes was synthesized via tandem α-propargylation-isomerization of chiral allenamides with moderate E/Z ratio. Reactivities of E-and Z-isomers were examined.

  通过具有中等 E/Z 比的手性丙二烯酰胺的串联 α-炔丙基化-异构化合成了一系列从头 3-酰氨基-二炔。检查了E-和Z-异构体的反应性。
• Highly Stereoselective [4 + 3] Cycloadditions of Nitrogen-Stabilized Oxyallyl Cations with Pyrroles. An Approach to Parvineostemonine
  作者：Jennifer E. Antoline、Richard P. Hsung、Jian Huang、Zhenlei Song、Gang Li

  DOI：10.1021/ol070103n

  日期：2007.3.1

  [structure: see text]. A highly stereoselective [4 + 3] cycloaddition of N-substituted pyrroles with allenamide-derived nitrogen-stabilized chiral oxyallyl cations is described here. This method provides an approach for constructing tropinone alkaloids.

  [结构：见文字]。在此描述了N-取代的吡咯与烯丙酰胺衍生的氮稳定的手性氧基烯丙基阳离子的高度立体选择性[4 + 3]环加成。该方法提供了构建肌钙蛋白生物碱的方法。
• Inverse electron-demand aza-[4+2] cycloaddition reactions of allenamides
  作者：Craig R. Berry、Richard P. Hsung

  DOI：10.1016/j.tet.2004.05.117

  日期：2004.8

  An inverse electron-demand aza-[4+2] cycloaddition reaction of allenamides with 1-azadiene is described here. Effects of solvents on diastereoselectivity along with synthetic scopes and mechanistic insights are illustrated. Despite some synthetic limitations, this aza-[4+2] cycloaddition does provide a useful template for the synthesis of aza-glycoside related heterocycles.

  本文描述了烯丙酰胺与1-氮杂二烯的电子反需求氮杂-[4 + 2]环加成反应。说明了溶剂对非对映选择性的影响以及合成范围和机理的见解。尽管存在一些合成限制，但这种aza- [4 + 2]环加成的确为合成aza-糖苷相关的杂环提供了有用的模板。