(3S)-3--1-oxaspiro<4.5>deca-7,10-diene-2,8-dione | 146830-10-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (3S)-3--1-oxaspiro<4.5>deca-7,10-diene-2,8-dione
• 英文别名: (3S)-3-[Bis(benzyloxycarbonyl)amino]-1-oxaspiro[4.5]deca-7,10-diene-2,8-dione；benzyl N-[(3S)-2,8-dioxo-1-oxaspiro[4.5]deca-6,9-dien-3-yl]-N-phenylmethoxycarbonylcarbamate
• CAS: 146830-10-6
• 化学式: C₂₅H₂₁NO₇
• 分子量: 447.444
• InChiKey: VPRAKBDPZCIVMQ-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  99.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (3S)-3--1-oxaspiro<4.5>deca-7,10-diene-2,8-dione 在 palladium on activated charcoal 1,4-环己二烯 、 Kishi's radical inhibitor 、 间氯过氧苯甲酸 作用下， 反应 4.0h， 生成
  参考文献：
  名称：

  Stereoselective synthesis of the functionalized spirocyclic core of aranorosin

  摘要：

  Oxidative cyclization of L-tyrosine, stereoselective addition of an alpha-alkoxy organolithium reagent, and hydroxyl-directed diepoxidation are key steps in the first synthesis of the fully functionalized core of aranorosin.

  DOI：

  10.1021/jo00059a004
• 作为产物：
  描述：

  N-苄氧羰基-L-酪氨酸 在 4-二甲氨基吡啶 、 碘苯二乙酸 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 0.5h， 生成 (3S)-3--1-oxaspiro<4.5>deca-7,10-diene-2,8-dione
  参考文献：
  名称：

  Stereoselective synthesis of the functionalized spirocyclic core of aranorosin

  摘要：

  Oxidative cyclization of L-tyrosine, stereoselective addition of an alpha-alkoxy organolithium reagent, and hydroxyl-directed diepoxidation are key steps in the first synthesis of the fully functionalized core of aranorosin.

  DOI：

  10.1021/jo00059a004

文献信息

• 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.
• Stereoselective synthesis of the functionalized spirocyclic core of aranorosin
  作者：Peter Wipf、Yuntae Kim

  DOI：10.1021/jo00059a004

  日期：1993.3

  Oxidative cyclization of L-tyrosine, stereoselective addition of an alpha-alkoxy organolithium reagent, and hydroxyl-directed diepoxidation are key steps in the first synthesis of the fully functionalized core of aranorosin.