Methyl (2R^*,3R^*)-2-butyl-3-hydroxy-4-pentenoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl (2R^*,3R^*)-2-butyl-3-hydroxy-4-pentenoate
• 英文别名: methyl (2R*,3R*)-2-butyl-3-hydroxypent-4-enoate；methyl (2S)-2-[(1S)-1-hydroxyprop-2-enyl]hexanoate
• 化学式: C₁₀H₁₈O₃
• 分子量: 186.251
• InChiKey: UCKJFRKOTVXICQ-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl (2R^*,3R^*)-2-butyl-3-hydroxy-4-pentenoate 在 溴 作用下， 以 氯仿 为溶剂， 以59%的产率得到(2R^*,3S^*,4S^*)-4-(Bromomethyl)-2-butyl-3-hydroxy-4-butanolide
  参考文献：
  名称：

  High diastereoselective aldol reactions of cobalt-complexed and uncomplexed propynals with an O-silyl ketene O,S-acetal: highly stereoselective total syntheses of (.+-.)-blastmycinone and its three diastereoisomers from 3-(trimethylsilyl)propynal

  摘要：

  Total syntheses of (+/-)-blastmycinone (2) and its three diastereoisomers (3-5) are described. The syntheses involve highly stereoselective aldol reactions of cobalt-complexed propynal 6 and uncomplexed propynal 7 with O-silyl ketene O,S-acetal 8, which possesses an n-butyl tether, under Mukaiyama conditions. (+/-)-Blastmycinone (2) and its 2-epimer 3 were stereoselectively synthesized through chelation-controlled reduction, whereas (+/-)-3-epi- and 4-epiblastmycinone (5 and 4) were obtained in a highly stereocontrolled manner with bromolactonization as a key step.

  DOI：

  10.1021/jo00063a008
• 作为产物：
  描述：

  ((1-(tert-butylthio)hex-1-en-1-yl)oxy)trimethylsilane 在 Lindlar's catalyst 氢氟酸 、 四丁基氟化铵 、 氢气 、 silver trifluoroacetate 、 四氯化钛 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， -78.0~60.0 ℃ 、101.33 kPa 条件下， 反应 5.5h， 生成 Methyl (2R^*,3R^*)-2-butyl-3-hydroxy-4-pentenoate
  参考文献：
  名称：

  High diastereoselective aldol reactions of cobalt-complexed and uncomplexed propynals with an O-silyl ketene O,S-acetal: highly stereoselective total syntheses of (.+-.)-blastmycinone and its three diastereoisomers from 3-(trimethylsilyl)propynal

  摘要：

  Total syntheses of (+/-)-blastmycinone (2) and its three diastereoisomers (3-5) are described. The syntheses involve highly stereoselective aldol reactions of cobalt-complexed propynal 6 and uncomplexed propynal 7 with O-silyl ketene O,S-acetal 8, which possesses an n-butyl tether, under Mukaiyama conditions. (+/-)-Blastmycinone (2) and its 2-epimer 3 were stereoselectively synthesized through chelation-controlled reduction, whereas (+/-)-3-epi- and 4-epiblastmycinone (5 and 4) were obtained in a highly stereocontrolled manner with bromolactonization as a key step.

  DOI：

  10.1021/jo00063a008

文献信息

• Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α,β-Unsaturated Methylketones
  作者：Elisa Farber、Aleksandra Rudnitskaya、Santosh Keshipeddy、Kendricks S. Lao、José A. Gascón、Amy R. Howell

  DOI：10.1021/jo4014645

  日期：2013.11.15

  The first rearrangement of 2-methyleneoxetanes to alpha,beta-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, alpha-silyl-alpha,beta-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.