ethyl (S)-4-hydroxy-pent-2-ynoate | 156317-04-3

• 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: ethyl (S)-4-hydroxy-pent-2-ynoate
• 英文别名: 2-Pentynoic acid, 4-hydroxy-, ethyl ester, (4S)-；ethyl (4S)-4-hydroxypent-2-ynoate
• CAS: 156317-04-3
• 化学式: C₇H₁₀O₃
• 分子量: 142.155
• InChiKey: UHUSKECRWHTFMW-LURJTMIESA-N

物化性质

• 沸点：
  235.5±23.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  ethyl (S)-4-hydroxy-pent-2-ynoate 在 RhCl(PPh₃)3 (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride 、 氢气 作用下， 以 甲醇 、 乙醇 、 苯 为溶剂， 25.0 ℃ 、193.05 kPa 条件下， 反应 23.5h， 生成 (2S)-2-甲基-4-[12-[(2S)-2-甲基-5-氧代-2H-呋喃-4-基]十二烷基]-2H-呋喃-5-酮
  参考文献：
  名称：

  Trost, Barry M.; Müller, Thomas J. J.; Martinez, Jose, Journal of the American Chemical Society, 1995, vol. 117, # 7, p. 1888 - 1899

  摘要：

  DOI：
• 作为产物：
  描述：

  在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到ethyl (S)-4-hydroxy-pent-2-ynoate
  参考文献：
  名称：

  Enantioselective Synthesis of Spliceostatin E and Evaluation of Biological Activity

  摘要：

  An enantioselective total synthesis of spliceostatin E has been accomplished. The d-lactone unit A was constructed from readily available (R)-glycidyl alcohol using a ring-closing olefin metathesis as the key reaction. A cross-metathesis of ring A containing d-lactone and the functionalized tetrahydropyran B-ring provided spliceostatin E. Our biological evaluation of synthetic spliceostatin E revealed that it does not inhibit splicing in vitro and does not impact speckle morphology in cells. Spliceostatin E was reported to possess potent antitumor activity.

  DOI：

  10.1021/ol503127r

文献信息

• Interligand Interactions Dictate the Regioselectivity of<i>trans</i>-Hydrometalations and Related Reactions Catalyzed by [Cp*RuCl]. Hydrogen Bonding to a Chloride Ligand as a Steering Principle in Catalysis
  作者：Stephan M. Rummelt、Karin Radkowski、Dragoş-Adrian Roşca、Alois Fürstner

  DOI：10.1021/jacs.5b01475

  日期：2015.4.29

  mode in the presence of [Cp*Ru(MeCN)3]PF6 (1) as the catalyst; however, the regioselectivity is often poor with unsymmetrical substrates. This problem can be solved upon switching to a catalyst comprising a [Ru-Cl] bond, provided that the acetylene derivative carries a protic functional group. The R3M unit is then delivered with high selectivity to the alkyne-C atom proximal to this steering substituent

  在 [Cp*Ru(MeCN)3]PF6 (1) 作为催化剂的存在下，内炔与 R3M-H（M = Si、Ge、Sn）的反应遵循非常规的反式加成模式；然而，不对称底物的区域选择性通常很差。如果乙炔衍生物带有质子官能团，则该问题可以通过改用包含 [Ru-Cl] 键的催化剂来解决。然后，R3M 单元以高选择性传递到该控制取代基附近的炔烃-C 原子。这种导向效应源于极化的 [Ru-Cl] 键与质子取代基进行氢键合的能力，这有助于将炔烃上传、激活和锁定在配位球内。氯化物与 -MR3 中心的额外配位体接触将进入的试剂定位在匹配的方向，从而转化为高区域选择性。所提出的负载催化剂内的二次相互作用与大量制备和光谱数据以及固态新型钌 π 配合物 10 和 11 的结构一致。此外，还提出了 [Ru(σ-锡烷)] 配合物 (12a) 的第一个 X 射线结构，它确实具有外围 Ru-Cl……MR3 接触；该加合物也证实炔烃反式加成化学可能涉及
• Ruthenium-Catalyzed [2 + 2] Cycloadditions between Norbornene and Propargylic Alcohols or Their Derivatives
  作者：Gavin C. Tsui、Karine Villeneuve、Emily Carlson、William Tam

  DOI：10.1021/om500563h

  日期：2014.7.28

  Diastereoselective ruthenium-catalyzed [2 + 2] cycloadditions of norbornene and propargylic alcohols or their derivatives were investigated. The cycloadditions were found to be highly stereoselective, giving exo cycloadducts in moderate to excellent yields with diastereoselectivities up to 92:8. When a chiral propargylic alcohol was used in the cycloaddition, up to 80% ee of the [2 + 2] cycloadducts was

  研究了降冰片烯和炔丙醇或其衍生物的非对映选择性钌催化的[2 + 2]环加成反应。发现环加成物具有高度立体选择性，使外型环加成物具有中等至优异的产率，非对映选择性高达92：8。当在环加成中使用手性炔丙醇时，在醇氧化后，观察到高达80％ee的[2 + 2]环加合物。
• A new strategy for the synthesis of optically active benzylic fluorides and corresponding five-membered heteroaromatic analogues
  作者：Danielle Grée、René Grée

  DOI：10.1016/j.tetlet.2007.06.007

  日期：2007.7

  Benzylic fluorides, as well as five-membered heterocycles, have been obtained in high ee’s through cycloaddition reactions starting from easily accessible optically active propargylic fluorides.

  苯甲酸氟化物以及五元杂环已通过易于从光学活性的炔丙基氟化物开始的环加成反应，以高ee数获得。
• Asymmetric reductions of propargyl ketones
  作者：M. Mark midland、Alfonso tramontano、Aleksander kazubski、Richard S. graham、David J.S. tsai、Daniel B. cardin

  DOI：10.1016/s0040-4020(01)82422-4

  日期：1984.1

  Propargyl ketones are readily reduced by the asymmetric reducing agent B-3-pinanyl-9- borabicyclo[3.3.1]-nonane (Alpine-borane). The reagent prepared from (+)-α-pinene and 9-BBN provides the R enantiomer while the S enantiomer can be obtained from (-)-α-pinene. Alternatively the S enantiomer can be prepared from the reagent derived from 9-BBN and the benzyl ether of nopol (6,6-dimethyl-bicyclo[3.11

  炔丙基酮很容易被不对称还原剂B -3-pinanyl-9- borabicyclo [3.3.1]-壬烷（Alpine-borane）还原。由（+）-α-pine烯和9-BBN制备的试剂可提供R对映体，而S对映异构体可获自（-）-α-obtained烯。或者，S对映异构体可以由衍生自9-BBN和nopol的苄基醚（6，6-二甲基-双环[3.11。]庚-2-烯-2-乙醇）的试剂制备。获得高对映体诱导的限制因素通常是α--烯的对映体纯度。用100％对映体纯的α-pine烯，可获得基本上100％ee的炔丙醇。提出了导致这种显着选择的过渡态的预测合理化。炔丙醇的乙炔单元为转化为其他有用的旋光产物提供了方便的方法。说明了炔丙醇在合成光学活性的α-和β-取代的γ-内酯以及δ-内酯中的用途。
• Diastereoselective Ruthenium-Catalyzed [2+2] Cycloadditions between Bicyclic Alkenes and a Chiral Propargylic Alcohol and its Derivatives
  作者：William Tam、Karine Villeneuve、Robert W. Jordan

  DOI：10.1055/s-2003-42108

  日期：——

  ruthenium-catalyzed [2+2] cycloadditions of symmetrical bicyclic alkenes and a chiral propargylic alcohol or its derivatives were investigated. The cycloadditions were found to be highly chemo- and stereoselective giving anti-exocycloadducts in moderate to good yields. Diastereoselectivities of 58:42 to 84:16 were observed with chiral propargylic alcohol 2f and its derivatives 2a-g.

  研究了非对映选择性钌催化的对称双环烯烃和手性炔丙醇或其衍生物的 [2+2] 环加成反应。发现环加成具有高度的化学和立体选择性，以中等至良好的产率提供抗外环加合物。使用手性炔丙醇 2f 及其衍生物 2a-g 观察到 58:42 至 84:16 的非对映选择性。