<3(2'R),4S>-3-(2-Methyl-1-oxooctyl)-4-(phenylmethyl)-2-oxazolidinone | 152899-15-5

• 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: <3(2'R),4S>-3-(2-Methyl-1-oxooctyl)-4-(phenylmethyl)-2-oxazolidinone
• 英文别名: (3(2'R),4S)-3-(2-Methyl-1-oxooctyl)-4-(phenylmethyl)-2-oxazolidinone；(4S)-4-benzyl-3-[(2R)-2-methyloctanoyl]-1,3-oxazolidin-2-one
• CAS: 152899-15-5
• 化学式: C₁₉H₂₇NO₃
• 分子量: 317.428
• InChiKey: BXXWQQNFXCTKNV-WBVHZDCISA-N

物化性质

• 沸点：
  460.7±14.0 °C(Predicted)
• 密度：
  1.084±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 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：

  <3(2'R),4S>-3-(2-Methyl-1-oxooctyl)-4-(phenylmethyl)-2-oxazolidinone 在 lithium hydroxide 、 正丁基锂 、 双氧水 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 6.0h， 生成 (S)-4-苄基-3-丙酰基-2-噁唑烷酮
  参考文献：
  名称：

  Total synthesis and structure assignment of the antitumor antibiotic aranorosin

  摘要：

  The structurally unique antifungal and antitumor antibiotic aranorosin was prepared in a convergent, stereoselective sequence. Oxidative cyclization of N-protected L-tyrosine, followed by face-selective 1,2-addition of [(benzyloxy)methyl]lithium, Henbest oxidation in the presence of Kishi's radical inhibitor, and simultaneous N,O-deprotection led to an amino diol which was N-acylated with the fatty acid side-chain segment. After a low-temperature reduction of the lactone moiety to the lactol, the carbonyl function was regenerated under neutral conditions by diol cleavage with sodium periodate. Preparation of the acid side chain involved a diastereoselective imide alpha-alkylation directed by Evans' oxazolidinone auxiliary, followed by a series of Wittig-Horner chain extensions. Since the relative configuration at the C (6') position of the natural product had not been determined, we prepared both the (6'S) and the (6'R) isomers of aranorosin. Comparison of synthetic material with the reported spectral data for natural (-)-aranorosin, especially H-1 and C-13 NMR and [alpha]D, did not allow a definitive assignment. After purification of a sample of the isolated material from Pseudoarachniotus roseus, the corrected [alpha]D strongly indicated the (6'R)-stereochemistry for the natural compound. This assignment was confirmed by circular dichroism spectra for (6'S)- and (6'R)-aranorosin and the natural material.

  DOI：

  10.1021/jo00077a050
• 作为产物：
  描述：

  三氟甲磺酸己酯 、 (S)-4-苄基-3-丙酰基-2-噁唑烷酮 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以37%的产率得到<3(2'R),4S>-3-(2-Methyl-1-oxooctyl)-4-(phenylmethyl)-2-oxazolidinone
  参考文献：
  名称：

  Total synthesis and structure assignment of the antitumor antibiotic aranorosin

  摘要：

  The structurally unique antifungal and antitumor antibiotic aranorosin was prepared in a convergent, stereoselective sequence. Oxidative cyclization of N-protected L-tyrosine, followed by face-selective 1,2-addition of [(benzyloxy)methyl]lithium, Henbest oxidation in the presence of Kishi's radical inhibitor, and simultaneous N,O-deprotection led to an amino diol which was N-acylated with the fatty acid side-chain segment. After a low-temperature reduction of the lactone moiety to the lactol, the carbonyl function was regenerated under neutral conditions by diol cleavage with sodium periodate. Preparation of the acid side chain involved a diastereoselective imide alpha-alkylation directed by Evans' oxazolidinone auxiliary, followed by a series of Wittig-Horner chain extensions. Since the relative configuration at the C (6') position of the natural product had not been determined, we prepared both the (6'S) and the (6'R) isomers of aranorosin. Comparison of synthetic material with the reported spectral data for natural (-)-aranorosin, especially H-1 and C-13 NMR and [alpha]D, did not allow a definitive assignment. After purification of a sample of the isolated material from Pseudoarachniotus roseus, the corrected [alpha]D strongly indicated the (6'R)-stereochemistry for the natural compound. This assignment was confirmed by circular dichroism spectra for (6'S)- and (6'R)-aranorosin and the natural material.

  DOI：

  10.1021/jo00077a050

文献信息

• The total synthesis of the diepoxycyclohexanone antibiotic aranorosin and novel synthetic analogues
  作者：Alexander McKillop、Lee McLaren、Richard J. K. Taylor、Robert J. Watson、Norman J. Lewis

  DOI：10.1039/p19960001385

  日期：——

  A short synthesis of the novel antibiotic aranorosin in chiral form is described which employs (i) a novel hypervalent iodine-mediated oxidative hydroxylation of a tyrosinal derivative and (ii) a stereocontrolled cis-bisepoxidation in the key steps. A similar procedure was employed to prepare 6′-epiaranorosin, and hence establish the stereochemistry of the natural compound, and to prepare novel aranorosin

  描述了手性形式的新型抗生素阿糖胞苷的简短合成，其在关键步骤中采用了（i）酪氨酸衍生物的新型高价碘介导的氧化羟基化作用和（ii）立体控制的顺式-双环氧化。采用相似的方法制备6'-表皮阿糖胞苷，从而建立天然化合物的立体化学，并制备新的阿糖胞苷类似物。描述了一种有机金属路线，该路线产生了脱酰胺基芳族松香。
• Total synthesis and structure assignment of the antitumor antibiotic aranorosin
  作者：Peter Wipf、Yuntae Kim、Paul C. Fritch

  DOI：10.1021/jo00077a050

  日期：1993.12

  The structurally unique antifungal and antitumor antibiotic aranorosin was prepared in a convergent, stereoselective sequence. Oxidative cyclization of N-protected L-tyrosine, followed by face-selective 1,2-addition of [(benzyloxy)methyl]lithium, Henbest oxidation in the presence of Kishi's radical inhibitor, and simultaneous N,O-deprotection led to an amino diol which was N-acylated with the fatty acid side-chain segment. After a low-temperature reduction of the lactone moiety to the lactol, the carbonyl function was regenerated under neutral conditions by diol cleavage with sodium periodate. Preparation of the acid side chain involved a diastereoselective imide alpha-alkylation directed by Evans' oxazolidinone auxiliary, followed by a series of Wittig-Horner chain extensions. Since the relative configuration at the C (6') position of the natural product had not been determined, we prepared both the (6'S) and the (6'R) isomers of aranorosin. Comparison of synthetic material with the reported spectral data for natural (-)-aranorosin, especially H-1 and C-13 NMR and [alpha]D, did not allow a definitive assignment. After purification of a sample of the isolated material from Pseudoarachniotus roseus, the corrected [alpha]D strongly indicated the (6'R)-stereochemistry for the natural compound. This assignment was confirmed by circular dichroism spectra for (6'S)- and (6'R)-aranorosin and the natural material.