(2R,3S)-2-but-3'-enyltetrahydropyran-3-ol | 161946-36-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2R,3S)-2-but-3'-enyltetrahydropyran-3-ol
• 英文别名: (2R,3S)-2-but-3-enyloxan-3-ol
• CAS: 161946-36-7
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: BLMOSLKDICEXBD-DTWKUNHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  (2R,3S)-2-but-3'-enyltetrahydropyran-3-ol 在 咪唑 、 sodium tetrahydroborate 作用下， 生成 3-[(2R,3S)-3-(tert-butyldimethylsilanyloxy)tetrahydropyran-2-yl]propan-1-ol
  参考文献：
  名称：

  立体控制的ω-三丁基锡烷基醚醛的分子内环化。多环醚的6·7·7·6环体系的合成

  摘要：

  BF 3 .OEt 2介导的在碳链末端具有醛基的γ-氧代取代的烯丙基锡（1）的分子内环化以立体控制的方式进行，得到了7元的β-羟基环醚（2a）高非对映选择性。该方法被用于6·7·7·6环系统（3a）的合成。

  DOI：

  10.1016/0040-4039(91)85042-4
• 作为产物：
  描述：

  (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane 在 偶氮二异丁腈 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 12.0h， 生成 (2R,3S)-2-but-3'-enyltetrahydropyran-3-ol
  参考文献：
  名称：

  Ring-Closing Metathesis in the Synthesis of Large and Medium-Sized Oxacycles. Application to the Synthesis of Polyoxygenated Macrocycles

  摘要：

  Ring-closing olefin metathesis (RCM) catalyzed by Grubbs's ruthenium benzylidene complex 1 is applied to the synthesis of unsaturated rings ranging in size from seven to thirteen members in trans-fused polyether systems. Reaction occurs with great efficiency in the cyclization of oxepene and oxocene rings, but as ring size increases, yields drop. The influence of the final double bond position is also studied. Better yields and milder reaction conditions are observed when an additional oxygen atom is introduced on the diene. This feature has promoted the application of this reaction to the synthesis of polyoxygenated macrocycles (with sizes ranging from 15 to 21 members), with excellent results.

  DOI：

  10.1021/jo9901438

文献信息

• Stereoselective Synthesis of 2,6-<i>Cis</i>-Substituted Tetrahydropyrans: Brønsted Acid-Catalyzed Intramolecular Oxa-Conjugate Cyclization of α,β-Unsaturated Ester Surrogates
  作者：Haruhiko Fuwa、Naoki Ichinokawa、Kenkichi Noto、Makoto Sasaki

  DOI：10.1021/jo202179s

  日期：2012.3.16

  for the synthesis of tetrahydropyrans. However, it has been known that stereochemical outcome of IOCC depends on the local structure of substrates and sometimes requires harsh reaction conditions and/or prolonged reaction times for selective formation of 2,6-cis-substituted tetrahydropyrans. These shortcomings limit the feasibility of IOCC in the context of complex natural product synthesis. In this

  α，β-不饱和羰基化合物的分子内氧杂共轭环化（IOCC），是通过用碱去质子化触发的，是合成四氢吡喃的直接方法。然而，已知IOCC的立体化学结果取决于底物的局部结构，并且有时需要苛刻的反应条件和/或延长的反应时间以选择性地形成2，6-顺式取代的四氢吡喃。这些缺点限制了IOCC在复杂的天然产物合成中的可行性。在本文中，我们描述了在温和的反应条件下，布朗斯台德酸催化的α，β-不饱和酯替代物（例如，α，β-不饱和硫代酯，恶唑烷酮酰亚胺和吡咯酰胺）的IOCC，可提供一系列合成上通用的2， 6-顺式取代的四氢吡喃衍生物，具有良好至出色的立体选择性（dr为7：1至> 20：1）。发现这些α，β-不饱和羰基化合物比通常对布朗斯台德酸催化的分子内氧杂-共轭物加成没有反应性的相应的含氧酸酯有更高的反应性。产品四氢吡喃类化合物可以有效地转化为各种衍生物，突出了我们方法学的有用性。
• Diastereoselective Ring-Closing Metathesis as a Means to Construct Medium-Sized Cyclic Ethers: Application to the Synthesis of a Photoactivatable Gambierol Derivative
  作者：Yu Onodera、Kazuaki Hirota、Yuto Suga、Keiichi Konoki、Mari Yotsu-Yamashita、Makoto Sasaki、Haruhiko Fuwa

  DOI：10.1021/acs.joc.6b01302

  日期：2016.9.16

  describes a concise synthesis of six- to eight-membered α,α′-substituted cyclic ethers by exploiting diastereoselective ring-closing metathesis (RCM) of 1,4-pentadien-3-yl ether derivatives. The RCM precursors could be efficiently prepared via a vinylation of the corresponding α-acetoxy ether derivatives using divinylzinc. Diastereoselective RCM of 1,4-pentadien-3-yl ether derivatives afforded a series

  本文介绍了通过利用1,4-戊二烯-3-基醚衍生物的非对映选择性闭环复分解（RCM）合成六至八元的α，α'-取代的环醚的方法。可以使用二乙烯基锌通过相应的α-乙酰氧基醚衍生物的乙烯基化来有效地制备RCM前体。1,4-戊二烯-3-基醚衍生物的非对映选择性RCM提供一系列具有中等至良好非对映选择性的六至八元α，α'-取代的环状醚。非对映选择性RCM的立体化学结果似乎取决于所锻造的环的结构。六元和七元环醚的非对映选择性似乎在很大程度上受动力学控制，而与催化剂的反应性无关，而八元环醚的催化活性可以控制。最后，将非对映选择性RCM化学方法用于合成生物素标记的甘比罗尔可光活化衍生物。
• Biosynthesis-Inspired Intramolecular Oxa-Conjugate Cyclization of α,β-Unsaturated Thioesters: Stereoselective Synthesis of 2,6-<i>cis</i>-Substituted Tetrahydropyrans
  作者：Haruhiko Fuwa、Kenkichi Noto、Makoto Sasaki

  DOI：10.1021/ol200333p

  日期：2011.4.1

  Intramolecular oxa-conjugate cyclization of alpha,beta-unsaturated thioesters under Bronsted acid catalysis, inspired by biosynthesis of polyketide natural products, provides a variety of 2,6-cis-substituted tetrahydropyran derivatives with excellent diastereoselectivities. An added bonus of this methodology is that the product tetrahydropyrans could be readily elaborated to various derivatives by exploiting the unique reactivity of the thioester group.
• Stereoselective Synthesis of Cyclic Ethers by Intramolecular Trapping of Dicobalt Hexacarbonyl-Stabilized Propargylic Cations
  作者：Juan M. Betancort、Tomás Martín、José M. Palazón、Víctor S. Martín

  DOI：10.1021/jo0340556

  日期：2003.4.1

  The intramolecular attack of a hydroxy group on an exo-biscobalthexacarbonyl propargylic cation provides cyclic ethers with six- to nine-membered rings. The scope and limitations of the methodology are described. The reaction is stereoselective when additional stereocenters are present, providing iterative methodology to access ladder-like cyclic ethers.
• Ring-Closing Metathesis in the Synthesis of Large and Medium-Sized Oxacycles. Application to the Synthesis of Polyoxygenated Macrocycles
  作者：Mercedes Delgado、Julio D. Martín

  DOI：10.1021/jo9901438

  日期：1999.6.1

  Ring-closing olefin metathesis (RCM) catalyzed by Grubbs's ruthenium benzylidene complex 1 is applied to the synthesis of unsaturated rings ranging in size from seven to thirteen members in trans-fused polyether systems. Reaction occurs with great efficiency in the cyclization of oxepene and oxocene rings, but as ring size increases, yields drop. The influence of the final double bond position is also studied. Better yields and milder reaction conditions are observed when an additional oxygen atom is introduced on the diene. This feature has promoted the application of this reaction to the synthesis of polyoxygenated macrocycles (with sizes ranging from 15 to 21 members), with excellent results.