(2R,3S)-tert-butyldimethyl-(2-pent-4'-enyltetrahydropyran-3-yloxy)silane | 234111-60-5

• 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)-tert-butyldimethyl-(2-pent-4'-enyltetrahydropyran-3-yloxy)silane
• 英文别名: tert-butyl-dimethyl-[(2R,3S)-2-pent-4-enyloxan-3-yl]oxysilane
• CAS: 234111-60-5
• 化学式: C₁₆H₃₂O₂Si
• 分子量: 284.514
• InChiKey: ACLNNYGTCPAPJH-CABCVRRESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,3S)-tert-butyldimethyl-(2-pent-4'-enyltetrahydropyran-3-yloxy)silane 在 四丁基氟化铵 、 四丁基碘化铵 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 (2R,3S)-2-pent-4"-enyl-3-pent-4'-enyloxytetrahydropyran
  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
• 作为产物：
  描述：

  (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane 在 盐酸 、 sodium tetrahydroborate 、 偶氮二异丁腈 、 potassium tert-butylate 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲醇 、 二甲基亚砜 、 苯 为溶剂， 反应 11.5h， 生成 (2R,3S)-tert-butyldimethyl-(2-pent-4'-enyltetrahydropyran-3-yloxy)silane
  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 Medium-Sized Cyclic Ethers: Application of <i>C</i>-Glycosylation Chemistry to Seven- to Nine-Membered Lactone-Derived Thioacetals and Their Sulfone Counterparts
  作者：Yuto Suga、Haruhiko Fuwa、Makoto Sasaki

  DOI：10.1021/jo4025545

  日期：2014.2.21

  Stereoselective synthesis of α,α′-substituted medium-sized cyclic ethers has been achieved by means of nucleophilic substitution of the corresponding lactone-derived thioacetals and their sulfone counterparts. Nucleophilic substitution of medium-sized lactone-derived thioacetals could be achieved efficiently either by (i) activation with NIS/TMSOTf in the presence of allyltrimethylsilane or TMSCN or

  已经通过相应的内酯衍生的硫缩醛及其砜对应物的亲核取代，实现了α，α'-取代的中型环状醚的立体选择性合成。中型内酯衍生的硫缩醛的亲核取代可以通过（i）在烯丙基三甲基硅烷或TMSCN存在下用NIS / TMSOTf活化，或（ii）氧化成相应的砜，然后用适当的有机金属物质处理来有效地实现作为二乙烯基锌或二甲基（2-苯基乙炔基）铝。有趣的是，发现立体化学结果在很大程度上取决于底物的局部结构。在某些情况下，在过渡状态下形成的gauche空间相互作用被认为是所观察到的非对映选择性的原因。
• 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.