4-O-benzoyl-2-O-benzyl-1,2-O-isopropylidene-L-threitol | 94451-15-7

• 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: 4-O-benzoyl-2-O-benzyl-1,2-O-isopropylidene-L-threitol
• 英文别名: [(2S)-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-phenylmethoxyethyl] benzoate
• CAS: 94451-15-7
• 化学式: C₂₁H₂₄O₅
• 分子量: 356.419
• InChiKey: HODFJGHFWSOTMO-OALUTQOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-O-benzoyl-2-O-benzyl-1,2-O-isopropylidene-L-threitol 在 咪唑 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 4.0h， 生成 Benzoic acid (2S,3S)-2-benzyloxy-4-(tert-butyl-dimethyl-silanyloxy)-3-hydroxy-butyl ester
  参考文献：
  名称：

  Visible Light Initiated Photosensitized Electron Transfer Cyclizations of Aldehydes and Ketones to Tethered α,β-Unsaturated Esters:  Stereoselective Synthesis of Optically Pure C-Furanosides

  摘要：

  Photosensitized one-electron reductive activation of aldehydes/ketones tethered with activated olefins leads to efficient cyclization to give diastereoselective cycloalkanols in high yield. The activation is promoted by secondary and dark electron transfer from visible light (405 nm) initiated photosensitized electron transfer generated 9,10-dicyanoanthracene radical anion (DCA(.-)). The DCA(.-) is produced by electron transfer using either triphenylphosphine (Ph3P) as sacrificial electron donor (PS-A) or 1,5-dimethoxynaphthalene (DMN) as primary electron donor and ascorbic acid as sacrificial electron donor (PS-B), to light-absorbing DCA. The cyclization is suggested to involve ketyl radical intermediate. High trans diastereoselectivity is observed during the formation of cycloalkanols. This cyclization strategy is further extended for the stereoselective synthesis of optically pure C-furanoside (41), starting from naturally occuring L-tartaric acid. The stereochemistry of 41 is suggested based on the single-crystal X-ray diffraction data.

  DOI：

  10.1021/jo9702812
• 作为产物：
  描述：

  2-O-benzyl-L-threitol 在 吡啶 、 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 生成 4-O-benzoyl-2-O-benzyl-1,2-O-isopropylidene-L-threitol
  参考文献：
  名称：

  Visible Light Initiated Photosensitized Electron Transfer Cyclizations of Aldehydes and Ketones to Tethered α,β-Unsaturated Esters:  Stereoselective Synthesis of Optically Pure C-Furanosides

  摘要：

  Photosensitized one-electron reductive activation of aldehydes/ketones tethered with activated olefins leads to efficient cyclization to give diastereoselective cycloalkanols in high yield. The activation is promoted by secondary and dark electron transfer from visible light (405 nm) initiated photosensitized electron transfer generated 9,10-dicyanoanthracene radical anion (DCA(.-)). The DCA(.-) is produced by electron transfer using either triphenylphosphine (Ph3P) as sacrificial electron donor (PS-A) or 1,5-dimethoxynaphthalene (DMN) as primary electron donor and ascorbic acid as sacrificial electron donor (PS-B), to light-absorbing DCA. The cyclization is suggested to involve ketyl radical intermediate. High trans diastereoselectivity is observed during the formation of cycloalkanols. This cyclization strategy is further extended for the stereoselective synthesis of optically pure C-furanoside (41), starting from naturally occuring L-tartaric acid. The stereochemistry of 41 is suggested based on the single-crystal X-ray diffraction data.

  DOI：

  10.1021/jo9702812

文献信息

• Biomimetic Total Synthesis of ( – )-Aplysistatin
  作者：Akira Tanaka、Soichiro Otsuka、Kyohei Yamashita

  DOI：10.1080/00021369.1984.10866525

  日期：1984.10

  A biomimetic synthesis of ( – )-aplysistatin (1) is described. The Wittig reaction of the keto ester 5 with homogeranyl triphenylphosphonium ylid gave the desired intermediate 3. Successive treatment of 3 with activated manganese dioxide, sodium chlorite and aq. trifluoroacetic acid led to the unsaturated β-hydroxy lactone 2, which was subjected to brominative cyclization to yield ( –)-aplysistatin (1).

  描述了一种仿生合成 ( – )-aplysistatin (1) 的方法。酮酯 5 与同源香叶基三苯基膦阳离子反应生成所需的中间体 3。随后对中间体 3 依次进行活化锰氧化物、氯酸钠和水合三氟乙酸的处理，得到不饱和的β-羟基内酯 2，随后对其进行溴化环化反应，最终得到 ( – )-aplysistatin (1)。