(4S,5R)-5-(3-acetoxy-4-benzyloxyphenyl)-2-(4-methoxyphenyl)-3-methyloxazolidine-4-carboxylic acid methyl ester | 821006-10-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚酯
• 英文名称: (4S,5R)-5-(3-acetoxy-4-benzyloxyphenyl)-2-(4-methoxyphenyl)-3-methyloxazolidine-4-carboxylic acid methyl ester
• 英文别名: methyl (4S,5R)-5-(3-acetyloxy-4-phenylmethoxyphenyl)-2-(4-methoxyphenyl)-3-methyl-1,3-oxazolidine-4-carboxylate
• CAS: 821006-10-4
• 化学式: C₂₈H₂₉NO₇
• 分子量: 491.541
• InChiKey: AXYAKQNWSSYZBK-AJRFNQODSA-N

物化性质

• 沸点：
  593.2±50.0 °C(Predicted)
• 密度：
  1.219±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  36
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  83.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (4S,5R)-5-(3-acetoxy-4-benzyloxyphenyl)-2-(4-methoxyphenyl)-3-methyloxazolidine-4-carboxylic acid methyl ester 在 盐酸 、 lithium hydroxide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 生成 (2S,3R)-3-(4-benzyloxy-3-hydroxyphenyl)-2-(tert-butoxycarbonylmethylamino)-3-hydroxypropionic acid benzyl ester
  参考文献：
  名称：

  A Convergent Total Synthesis of Ustiloxin D via an Unprecedented Copper-Catalyzed Ethynyl Aziridine Ring-Opening by Phenol Derivatives

  摘要：

  The ustiloxins are a family of heterodetic cyclopeptides that have been isolated from the water extracts of false smut balls on the panicles of rice plants caused by the fungus Ustilaginoidea virens. A concise total synthesis of ustiloxin D has been achieved via an unprecedented ethynyl aziridine ring-opening of phenol derivatives. The longest linear sequence of the synthesis is 15 steps from commercially available compounds.

  DOI：

  10.1021/ol052287g
• 作为产物：
  描述：

  在 sodium tetrahydroborate 作用下， 生成 (4S,5R)-5-(3-acetoxy-4-benzyloxyphenyl)-2-(4-methoxyphenyl)-3-methyloxazolidine-4-carboxylic acid methyl ester
  参考文献：
  名称：

  A Convergent Total Synthesis of Ustiloxin D via an Unprecedented Copper-Catalyzed Ethynyl Aziridine Ring-Opening by Phenol Derivatives

  摘要：

  The ustiloxins are a family of heterodetic cyclopeptides that have been isolated from the water extracts of false smut balls on the panicles of rice plants caused by the fungus Ustilaginoidea virens. A concise total synthesis of ustiloxin D has been achieved via an unprecedented ethynyl aziridine ring-opening of phenol derivatives. The longest linear sequence of the synthesis is 15 steps from commercially available compounds.

  DOI：

  10.1021/ol052287g

文献信息

• Evolution of the Total Syntheses of Ustiloxin Natural Products and Their Analogues
  作者：Pixu Li、Cory D. Evans、Yongzhong Wu、Bin Cao、Ernest Hamel、Madeleine M. Joullié

  DOI：10.1021/ja710363p

  日期：2008.2.1

  synthetically challenging chiral tertiary alkyl-aryl ether linkage. The first total synthesis of ustiloxin D was achieved in 31 linear steps using an S(N)Ar reaction. An NOE study of this synthetic product showed that ustiloxin D existed as a single atropisomer. Subsequently, highly concise and convergent syntheses of ustiloxins D and F were developed by utilizing a newly discovered ethynyl aziridine ring-opening

  Ustiloxins AF 是抗有丝分裂杂环肽，含有 13 元环状核心结构，具有合成上具有挑战性的手性叔烷基芳基醚键。使用 S(N)Ar 反应，通过 31 个线性步骤实现了 ustiloxin D 的首次全合成。该合成产品的 NOE 研究表明乌司洛辛 D 作为单一阻转异构体存在。随后，利用新发现的乙炔基氮丙啶开环反应，以 15 个步骤的最长线性序列开发了乌斯蒂洛辛 D 和 F 的高度简洁和收敛的合成方法。该方法进一步优化以实现更好的大环内酰胺化策略。通过第二代制备了乌斯蒂洛辛D、F和8个类似物（14-MeO-乌斯蒂洛辛D、4个C-6位氨基酸残基不同的类似物、以及3个(9R,10S)-表乌斯蒂洛辛类似物）路线。对这些化合物作为微管蛋白聚合抑制剂的评估表明，C-6 位的变化在一定程度上是可以容忍的。相反，C-9 甲氨基的 S 构型和游离酚羟基对于抑制微管蛋白聚合至关重要。
• Total Synthesis of Ustiloxin D and Considerations on the Origin of Selectivity of the Asymmetric Allylic Alkylation
  作者：Andrew M. Sawayama、Hiroko Tanaka、Thomas J. Wandless

  DOI：10.1021/jo048854f

  日期：2004.12.1

  C9. The chiral aryl−alkyl ether was assembled using a Pd-catalyzed asymmetric allylic alkylation that notably delivered a product with stereochemistry opposite to that predicted by precedent. The linear tetrapeptide was subsequently cyclized to produce ustiloxin D. The mechanistic origin of the allylic alkylation selectivity was further investigated, and a working hypothesis for the origin of the observed

  作为细胞周期检查点抑制剂研究的一部分，抗有丝分裂天然产物ustiloxin D的不对称合成已经完成。Salen-Al催化的醛醇缩合反应用于构建手性恶唑啉9（99％收率，98％ee），具有安装必要的1,2-氨基醇官能团以及为C9处所需的甲基氨基提供有效合成子的双重目的。手性芳基-烷基醚是使用Pd催化的不对称烯丙基烷基化反应组装而成的，该反应显着地提供了立体化学与先例所预测的相反的产物。随后将线性四肽环化以产生ustiloxinD。进一步研究了烯丙基烷基化选择性的机理起源，并提出了观察到的立体选择性起源的可行假设。