3-chloropropenyl pivaloate | 646995-60-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-chloropropenyl pivaloate
• 英文别名: 3-chloropropenyl pivalate；chloropropenyl pivalate；3-Chloroprop-1-en-1-yl 2,2-dimethylpropanoate；3-chloroprop-1-enyl 2,2-dimethylpropanoate
• CAS: 646995-60-0
• 化学式: C₈H₁₃ClO₂
• 分子量: 176.643
• InChiKey: JEDIZAFAMCVPDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-chloropropenyl pivaloate 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 1.0h， 生成 3-iodoprop-1-en-1-yl pivalate 、 3-iodoprop-1-en-1-yl pivalate
  参考文献：
  名称：

  铟和锌介导的受保护和未保护的Aldotetroses的酰氧基化反应-揭示了明显的非对映异构性和介导金属性能的根本差异。

  摘要：

  十多年前，未经保护的醛糖的酰氧基化首次被证实为还原糖的潜在的优雅的二碳同系物（通过臭氧分解）。但是，它在实际案例合成中的应用仍然很少。在如此成功的展示之后，我们回答了有关这一有吸引力的转变的几个悬而未决的问题，我们进行了深入的方法学重新调查。将未受保护和受保护形式的差向异构体四聚体l-赤藓糖和d-苏糖成功应用于铟以及锌介导的酰氧基烯丙基化，后者是未保护糖的首创。该研究很大程度上得益于这些更具异国情调的起始原料的选择，因为它可以对己糖产品进行明确的鉴定/定量，而后者可作为可靠的参考材料。观察到的非对映选择性表明对底物有很强的控制作用（O2处的立体化学），并详细研究了试剂结构对选择性的影响。相关保护和未保护结构之间存在强烈的面部非对映差异，并且铟和锌之间的性能表现出乎意料的显着差异。

  DOI：

  10.1021/acs.joc.7b03063

文献信息

• 3-Chloropropenyl pivaloate in organic synthesis: the first asymmetric catalytic entry to syn-alk-1-ene-3,4-diols
  作者：Marco Lombardo、Sebastiano Licciulli、Stefano Morganti、Claudio Trombini

  DOI：10.1039/b304485h

  日期：——

  The first asymmetric catalytic synthesis of syn-alk-1-ene-3,4-diols was developed; the regio-, diastereo- and enantioselective addition of 3-chloropropenyl pivaloate to aldehydes was made possible by exploiting Salen–Cr(II) species, in a catalytic version of the Nozaki–Hiyama–Kishi reaction.

  首次开发了合成烷-1-烯-3,4-二醇的不对称催化合成方法；在催化版 Nozaki-Hiyama-Kishi 反应中，利用 Salen-Cr(II) 物种，实现了 3-氯丙烯基特戊酸酯与醛的区域、非对映和对映选择性加成。
• 3-Bromozinc Propenyl Esters:  An Experimental and Theoretical Study of the Unique Stereocrossover Observed in Their Addition to Aromatic and Aliphatic Aldehydes
  作者：A. Bottoni、M. Lombardo、G. P. Miscione、J. B. Pujol Algué、C. Trombini

  DOI：10.1021/jo701661z

  日期：2008.1.1

  [GRAPHICS]We report the results of a combined experimental and theoretical study on the reaction of 3-bromopropenyl acetate in the presence of zinc with three different aldehydes (i.e., benzaldehyde, 2-methylpropanal, and cyclohexanecarboxaldehyde). A 80% de in favor of the anti product has been experimentally observed. with both saturated aldehydes, while for benzaldehyde, a 1:1 synlanti ratio has been found. DFT computations show the existence of three eta(1)-allylic organozinc complexes [gamma-(Z)-5a, gamma-(E)-5a, and alpha-5a], very close in energy. Only gamma-(Z)-5a and gamma-(E)-5a lead to the observed product. The computational investigation of the reaction of these allylic organozinc complexes with benzaldehyde and 2-methylpropanal demonstrates in both cases the existence of two competitive reaction paths leading to the syn and anti adducts, respectively. An anti preference has been found for 2-methylpropanal with both gamma-(Z)-5a and gamma-(E)-5a species (a diastereoselectivity larger than 80% is predicted), in agreement with the experiment. With benzaldehyde, while the reaction of gamma-(Z)-5a retains an anti-stereopreference (de = 70%), that involving gamma-(E)-5a is characterized by two degenerate transition states. In this case, the agreement between computations and experiments would be satisfactory under the assumption that the initial oxidative addition affords the gamma-(E)-5a zinc complex only. Additional MP2 computations have demonstrated that pi-stacking interactions can play a significant role in determining the relative energy of the transition states leading to the syn and anti products.
• Lombardo, Marco; Morganti, Stefano; Licciulli, Sebastiano, Synlett, 2003, # 1, p. 43 - 46
  作者：Lombardo, Marco、Morganti, Stefano、Licciulli, Sebastiano、Trombini, Claudio

  DOI：——

  日期：——
• Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal
  作者：Markus Draskovits、Christian Stanetty、Ian R. Baxendale、Marko D. Mihovilovic

  DOI：10.1021/acs.joc.7b03063

  日期：2018.3.2

  were successfully applied to the indium and also zinc-mediated acyloxyallylation, with the latter being a first for an unprotected sugar. The investigation largely benefited from the choice of these more exotic starting materials as it allowed unambiguous identification/quantification of the hexose-products which are available as authentic reference materials. The observed diastereoselectivities indicate

  十多年前，未经保护的醛糖的酰氧基化首次被证实为还原糖的潜在的优雅的二碳同系物（通过臭氧分解）。但是，它在实际案例合成中的应用仍然很少。在如此成功的展示之后，我们回答了有关这一有吸引力的转变的几个悬而未决的问题，我们进行了深入的方法学重新调查。将未受保护和受保护形式的差向异构体四聚体l-赤藓糖和d-苏糖成功应用于铟以及锌介导的酰氧基烯丙基化，后者是未保护糖的首创。该研究很大程度上得益于这些更具异国情调的起始原料的选择，因为它可以对己糖产品进行明确的鉴定/定量，而后者可作为可靠的参考材料。观察到的非对映选择性表明对底物有很强的控制作用（O2处的立体化学），并详细研究了试剂结构对选择性的影响。相关保护和未保护结构之间存在强烈的面部非对映差异，并且铟和锌之间的性能表现出乎意料的显着差异。