(2R,3S)-(2-but-3-enyl-tetrahydro-pyran-3-yloxy)-tert-butyl-dimethyl-silane | 139445-45-7

• 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-enyl-tetrahydro-pyran-3-yloxy)-tert-butyl-dimethyl-silane
• 英文别名: (2R,3S)-3-(tert-Butyldimethylsiloxy)-3,4,5,6-tetrahydro-2H-pyran-2-butene；(2R,3S)-(2-but-3'-enyltetrahydropyran-3-yloxy)-tert-butyldimethylsilane；[(2R,3S)-2-but-3-enyloxan-3-yl]oxy-tert-butyl-dimethylsilane
• CAS: 139445-45-7
• 化学式: C₁₅H₃₀O₂Si
• 分子量: 270.488
• InChiKey: VMEKUYPOILTIAS-KGLIPLIRSA-N

物化性质

• 沸点：
  295.6±33.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 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)-(2-but-3-enyl-tetrahydro-pyran-3-yloxy)-tert-butyl-dimethyl-silane 在 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：

  toluene-4-sulfonic acid (2'R,3'S)-3'-hydroxytetrahydropyran-2'-ylmethyl ester 在 咪唑 、 copper(I) bromide 作用下， 生成 (2R,3S)-(2-but-3-enyl-tetrahydro-pyran-3-yloxy)-tert-butyl-dimethyl-silane
  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

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。
• Efficient strategy for the iterative synthesis of trans-fused polycyclic ether via SmI2-induced reductive intramolecular cyclization
  作者：Nobuyuki Hori、Hiroko Matsukura、Goh Matsuo、Tadashi Nakata

  DOI：10.1016/s0040-4020(02)00042-x

  日期：2002.3

  A highly efficient strategy for the iterative synthesis of a trans-fused polycyclic ether ring system has been developed. The new iterative method involves SmI2-induced reductive intramolecular cyclization of an aldehyde and a β-alkoxy acrylate as the key step, producing a 2,3-trans-tetrahydropyran or oxepane ring. The syntheses of trans-fused 6,6,6-tricyclic, 6,7,6-tricyclic, and 6,7,7,6-tetracyclic

  已经开发出用于反式稠合多环醚环系统的迭代合成的高效策略。新的迭代方法涉及作为关键步骤的SmI 2诱导的醛和β-烷氧基丙烯酸酯的还原性分子内环化，生成2，3-反式-四氢吡喃或氧杂环丁烷环。基于新开发的方法，可以有效地实现反式稠合的6,6,6-三环醚，6,7,6-三环醚和6,7,7,6-四环醚的合成。
• Stereoselective syntheses of trans-fused 6,6- and 6,7-membered ether ring systems having an angular methyl group based on SmI2-induced reductive intramolecular cyclization
  作者：Goh Matsuo、Nobuyuki Hori、Tadashi Nakata

  DOI：10.1016/s0040-4039(99)01861-4

  日期：1999.12

  Highly stereoselective syntheses of trans-fused 6,6- and 6,7-membered ether ring systems having an angular methyl group were achieved based on SmI2-induced reductive intramolecular cyclizations of an aldehyde or a methyl ketone and a β-alkoxy acrylate.

  基于SmI 2诱导的醛或甲基酮和β-烷氧基丙烯酸酯的还原性分子内环化反应，实现了具有角甲基的反式稠合的6,6-和6,7-元醚环系统的高度立体选择性合成。
• Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations
  作者：Eleuterio Alvarez、Maria T. Diaz、Ricardo Perez、Jose L. Ravelo、Alicia Regueiro、Jose A. Vera、Dacil Zurita、Julio D. Martin

  DOI：10.1021/jo00089a034

  日期：1994.5

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.
• 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.