methyl 2-{(S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]hydroxymethyl}acrylate | 93714-49-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: methyl 2-{(S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]hydroxymethyl}acrylate
• 英文别名: methyl 2-[(S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]prop-2-enoate
• CAS: 93714-49-9
• 化学式: C₁₀H₁₆O₅
• 分子量: 216.234
• InChiKey: MDBWODYZTISSKP-SFYZADRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-{(S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]hydroxymethyl}acrylate 在 三氟乙酸 作用下， 以 水 为溶剂， 反应 2.0h， 以58%的产率得到(3S,4R)-2-methylene-3-hydroxy-4-(hydroxymethyl)-γ-butyrolactone
  参考文献：
  名称：

  来自 Baylis-Hillman 加合物的碳水化合物衍生物。2-Deoxy-2-C-methylene-D-erythro-pentono-1,4-lactone 的简单快速合成

  摘要：

  摘要描述了一种从手性 α-羟基醛获得的 Baylis-Hillman 加合物合成 α-亚甲基-δ-丁内酯的简单直接的方法。

  DOI：

  10.1081/scc-200026664
• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 三乙烯二胺 、 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate 作用下， 反应 4.0h， 以57%的产率得到methyl 2-{(S)-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]hydroxymethyl}acrylate
  参考文献：
  名称：

  来自 Baylis-Hillman 加合物的碳水化合物衍生物。2-Deoxy-2-C-methylene-D-erythro-pentono-1,4-lactone 的简单快速合成

  摘要：

  摘要描述了一种从手性 α-羟基醛获得的 Baylis-Hillman 加合物合成 α-亚甲基-δ-丁内酯的简单直接的方法。

  DOI：

  10.1081/scc-200026664

文献信息

• Acyl Radical Addition to Activated Olefins: A Stereocontrolled Route to Polysubstituted Tetrahydrofurans and Lactones, and Application to the Total Synthesis of (+)-No. 2106 A
  作者：Simon Grélaud、Jonathan Lusseau、Yannick Landais

  DOI：10.1002/ejoc.201601624

  日期：2017.3.10

  Addition of acyl radicals to Baylis‐Hillman adducts followed by acetalization and reduction with (Me3Si)3SiH provides the corresponding tetrahydrofurans with moderate 1,2‐ but high 1,3‐stereocontrol. Similar addition to methylenelactones was shown to afford tetrahydrofuran–lactones with high stereocontrol, this strategy being then applied to the total synthesis of (+)‐no. 2106 A.

  在Baylis-Hillman加合物上添加酰基自由基，然后进行缩醛化并用（Me 3 Si）3 SiH还原，可得到相应的具有中等1,2-但高1,3-立体控制的四氢呋喃。研究表明，向亚甲基内酯中添加类似物可提供具有高度立体控制的四氢呋喃内酯，然后将该策略应用于（+）-no的全合成。2106A。
• Synthesis of α‐Chiral Butyrolactones by Highly Stereoselective Radical Transfer or Sequential Asymmetric Alkylations: Concise Preparation of Leupyrrin Moieties
  作者：Michael Schrempp、Sebastian Thiede、Daniel Herkommer、Andreas Gansäuer、Dirk Menche

  DOI：10.1002/chem.201502263

  日期：2015.11.2

  and B1, two novel stereoselective methods for the highly concise synthesis of densely substituted α‐chiral butyrolactones are reported. The first approach relies on an innovative three‐step TiIII‐catalyzed radical reaction that proceeds with excellent chemo‐, regio‐, and stereoselectivity. The alternative route utilizes sequential asymmetric alkylations and enables asymmetric synthesis of the authentic

  受生物活性天然代谢产物亮丙瑞林A 1和B 1的启发，报道了两种新颖的立体选择性方法，用于高度简洁地合成密集取代的α-手性丁内酯。第一种方法依赖于创新的三步Ti III催化的自由基反应，该反应具有出色的化学，区域和立体选择性。另一种途径是利用顺序的不对称烷基化，并从市售底物仅需四个步骤就可以实现不对称合成亮丙啶的真实α-四取代丁内酯基序。
• Manickum, Thavrin; Ross, Gregory H. P., South African Journal of Chemistry, 1994, vol. 47, # 1, p. 1 - 16
  作者：Manickum, Thavrin、Ross, Gregory H. P.

  DOI：——

  日期：——
• Improved catalysis of Morita–Baylis–Hillman reaction. The strong synergic effect using both an imidazolic ionic liquid and a temperature
  作者：Ricardo S. Porto、Giovanni W. Amarante、Mayra Cavallaro、Ronei J. Poppi、Fernando Coelho

  DOI：10.1016/j.tetlet.2008.12.089

  日期：2009.3

  The effect of different catalytic conditions for the Morita-Baylis-Hillman reaction has been evaluated both experimentally and by chemometry. The use of either ultrasound at 0 degrees C, ultrasound with an imidazolic ionic liquid at 0 degrees C or the ionic liquid catalyst at 0 and 50 degrees C was systematically tested. A strong synergic effect, which significantly increases the reaction rates and yields, was observed when the reactions were performed using an imidazolic ionic liquid catalyst at both 0 and 50 degrees C. (C) 2008 Elsevier Ltd. All rights reserved.
• Reversal of stereoselectivity of Mg(II) catalysed 1,3-dipolar cycloaddition. Acceleration of cycloaddition by microwave irradiation
  作者：Peter Micˇúch、L'ubor Fisˇera、MichałK. Cyrański、Tadeusz M. Krygowski

  DOI：10.1016/s0040-4039(98)80049-x

  日期：1999.1

  1,3-Dipolar cycloadditions of mesitonitrile oxide to Baylis-Hillman adducts (beta-hydroxy-alpha-methylene esters) proceed regioselectively in good yields. Addition of a Grignard reagent reverses the diastereoselectivity of the cycloaddition. Microwave irradiation strongly accelerates the reaction with only a small effect on its diastereoisomeric excess. (C) 1998 Elsevier Science Ltd. All rights reserved.

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