(2Z)-3-甲基-4-(苄氧基)-2-丁烯-1-醇 | 62311-47-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (2Z)-3-甲基-4-(苄氧基)-2-丁烯-1-醇
• 英文名称: (Z)-4-(benzyloxy)-3-methylbut-2-en-1-ol
• 英文别名: (Z)-3-methyl-4-benzyloxybut-2-enol；(Z)-3-methyl-4-phenylmethoxybut-2-en-1-ol
• CAS: 62311-47-1
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: XMVUEHYAOORWLV-XFFZJAGNSA-N

物化性质

• 溶解度：
  溶于氯仿

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2Z)-3-甲基-4-(苄氧基)-2-丁烯-1-醇 在 吡啶 、 碘 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 作用下， 以 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 11.5h， 生成 dibenzyl ((2S,3R)-2-methyl-1-benzyloxy-2,3-dihydroxy-4-butyl) phosphate
  参考文献：
  名称：

  Synthesis of 4-Diphosphocytidyl-2-C-methyl-d-erythritol and 2-C-Methyl-d-erythritol-4-phosphate

  摘要：

  2-C-Methyl-D-erythritol 4-phosphate (MEP, 2) and 4-diphosphocytidyl-2-C-methyl-D-erythritol (CDPME, 3) are metabolites in the MEP pathway for biosynthesis of isoprenoid compounds in bacteria, plant chloroplasts, and algae. The free phosphoacid of 2 was prepared from benzyloxyacetone in five steps with an overall yield of 27% and an enantiomeric ratio (er) of 75:25. Following titration to the corresponding tributylammonium salt, 2 was coupled to cytidine 5'-monophosphate using a protocol originally developed for synthesis of base-sensitive nucleoside diphosphate sugars to give 3 in 40% yield, following purification by size exclusion chromatography.

  DOI：

  10.1021/jo025736o
• 作为产物：
  描述：

  苄氧基丙酮 在 lithium aluminium tetrahydride 、 potassium hydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 38.25h， 生成 (2Z)-3-甲基-4-(苄氧基)-2-丁烯-1-醇
  参考文献：
  名称：

  Synthesis of 4-Diphosphocytidyl-2-C-methyl-d-erythritol and 2-C-Methyl-d-erythritol-4-phosphate

  摘要：

  2-C-Methyl-D-erythritol 4-phosphate (MEP, 2) and 4-diphosphocytidyl-2-C-methyl-D-erythritol (CDPME, 3) are metabolites in the MEP pathway for biosynthesis of isoprenoid compounds in bacteria, plant chloroplasts, and algae. The free phosphoacid of 2 was prepared from benzyloxyacetone in five steps with an overall yield of 27% and an enantiomeric ratio (er) of 75:25. Following titration to the corresponding tributylammonium salt, 2 was coupled to cytidine 5'-monophosphate using a protocol originally developed for synthesis of base-sensitive nucleoside diphosphate sugars to give 3 in 40% yield, following purification by size exclusion chromatography.

  DOI：

  10.1021/jo025736o

文献信息

• The Asymmetric Aza-Claisen Rearrangement: Development of Widely Applicable Pentaphenylferrocenyl Palladacycle Catalysts
  作者：Daniel F. Fischer、Assem Barakat、Zhuo-qun Xin、Matthias E. Weiss、René Peters

  DOI：10.1002/chem.200900712

  日期：2009.9.7

  has a broader substrate tolerance than all previously known catalyst systems for asymmetric aza‐Claisen rearrangements. Our investigations also reveal that subtle changes can have a big impact on the activity. With the enhanced catalyst activity, the asymmetric aza‐Claisen rearrangement has a very broad scope: the methodology not only allows the formation of highly enantioenriched primary allylic amines

  已经进行了系统的研究，以开发用于三卤代乙亚氨酸盐的不对称氮杂-克莱森重排的高效催化剂。在本文中，我们描述了逐步发展这些催化剂体系的过程，涉及到四个不同的催化剂世代，最终导致了平面手性五苯基二茂铁基恶唑啉四氢环庚烷的发展。与所有先前已知的非对称氮杂-克莱森重排催化剂体系相比，该络合物具有更高的反应活性和更大的底物耐受性。我们的调查还显示，细微的变化会对活动产生重大影响。随着催化剂活性的增强，不对称氮杂-克莱森重排的范围非常广泛：该方法不仅可以形成高度对映体富集的伯烯丙基胺，而且还可以形成仲胺和叔胺。具有N-取代的季立体中心的烯丙基胺也很容易获得。反应条件可以耐受许多重要的官能团，从而提供了对有价值的功能化结构单元的立体选择性途径，例如，用于合成非天然氨基酸。我们的结果表明，面选择性烯烃配位是确定对映选择性的步骤，几乎仅由平面手性元素控制。
• Stereospecific Asymmetric Synthesis of Tertiary Allylic Alcohol Derivatives by Catalytic [2,3]‐Meisenheimer Rearrangements
  作者：Xin Yu、Nick Wannenmacher、René Peters

  DOI：10.1002/anie.202001725

  日期：2020.6.26

  Chiral acyclic tertiary allylic alcohols are very important synthetic building blocks, but their enantioselective synthesis is often challenging. A major limitation in catalytic asymmetric 1,2‐addition approaches to ketones is the enantioface differentiation by steric distinction of both ketone residues. Herein we report the development of a catalytic asymmetric Meisenheimer rearrangement to overcome

  手性无环叔烯丙基醇是非常重要的合成基石，但其对映选择性合成通常具有挑战性。酮的催化不对称1,2-加成方法的主要局限性是通过两个酮残基的空间区别来区分对映体。本文中，我们报道了催化不对称迈森海默重排技术的发展，以克服该问题，因为它以立体定向方式进行。这也允许高对映选择性形成产物，其中所产生的四取代的立体中心的残基显示出类似的空间需求。发现低的催化剂负载量是足够的，并且反应条件温和到足以耐受甚至高反应性的官能团，例如可烯化的醛，伯甲苯磺酸酯或环氧化物。
• Synthesis of 2-substituted bicyclo[1.1.0]butanes <i>via</i> zincocyclopropanation using bromoform as the carbenoid precursor
  作者：Léa Thai-Savard、André B. Charette

  DOI：10.1039/d3cc00335c

  日期：——

  Through a revisited Simmons–Smith type zincocyclopropanation using bromoform as the carbenoid source, the synthesis of 2-, 2,2- and 2,4-substituted bicyclo[1.1.0]butanes is reported. Few antecedents of the derivatives have yet been described. Ultimately, the underexplored scaffolds exhibited a complete discrepency of reactivity.

  通过使用三溴甲烷作为类胡萝卜素来源重新审视的 Simmons-Smith 型锌基环丙烷化反应，报道了 2-、2,2- 和 2,4- 取代的双环[1.1.0] 丁烷的合成。几乎没有描述衍生物的前因。最终，未充分探索的支架表现出完全不同的反应性。
• Asymmetric Formation of Allylic Amines with N-Substituted Quaternary Stereocenters by PdII-Catalyzed Aza-Claisen Rearrangements
  作者：Daniel F. Fischer、Zhuo-qun Xin、René Peters

  DOI：10.1002/anie.200702086

  日期：2007.10.8
• Synthesis of 4-Diphosphocytidyl-2-<i>C</i>-methyl-<scp>d</scp>-erythritol and 2-<i>C</i>-Methyl-<scp>d</scp>-erythritol-4-phosphate
  作者：Andrew T. Koppisch、C. Dale Poulter

  DOI：10.1021/jo025736o

  日期：2002.7.1

  2-C-Methyl-D-erythritol 4-phosphate (MEP, 2) and 4-diphosphocytidyl-2-C-methyl-D-erythritol (CDPME, 3) are metabolites in the MEP pathway for biosynthesis of isoprenoid compounds in bacteria, plant chloroplasts, and algae. The free phosphoacid of 2 was prepared from benzyloxyacetone in five steps with an overall yield of 27% and an enantiomeric ratio (er) of 75:25. Following titration to the corresponding tributylammonium salt, 2 was coupled to cytidine 5'-monophosphate using a protocol originally developed for synthesis of base-sensitive nucleoside diphosphate sugars to give 3 in 40% yield, following purification by size exclusion chromatography.