(Z)-6-(tert-butyldiphenylsiloxy)-4-penten-1-ol | 307497-58-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (Z)-6-(tert-butyldiphenylsiloxy)-4-penten-1-ol
• 英文别名: (4Z)-6-(tert-butyldiphenylsilyloxy)-4-hexen-1-ol；(Z)-6-[tert-butyl(diphenyl)silyl]oxyhex-4-en-1-ol
• CAS: 307497-58-1
• 化学式: C₂₂H₃₀O₂Si
• 分子量: 354.565
• InChiKey: GNXYKGCFTVIVRC-ACAGNQJTSA-N

物化性质

• 沸点：
  436.4±45.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  25
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  (Z)-6-(tert-butyldiphenylsiloxy)-4-penten-1-ol 在 正丁基锂 、 pyridine-SO3 complex 、 二甲基亚砜 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.58h， 生成 (Z)-8-(tert-butyldiphenylsiloxy)-6-octen-2-yn-1-ol
  参考文献：
  名称：

  Base-Catalyzed Endo-Mode Cyclization of Allenes:  Easy Preparation of Five- to Nine-Membered Oxacycles

  摘要：

  A reliable and efficient procedure for constructing five- to eight-membered oxacycles has been developed. Allenes with both a phosphoryl group and a suitable delta-hydroxyalkyl side chain at the Cl-position underwent an endo mode ring-closing reaction to give five- to seven-membered oxacycles. Changing the phosphoryl group to a phosphono functionality facilitated the preparation of eight-membered congeners. Introduction of a cis double bond to the alkyl side chain of the starting allenes made possible the easy formation of medium-sized oxacycles, such as the dihydrooxocin and tetrahydrooxonin frameworks, regardless of the electron-withdrawing group (POPh2, PO(OEt)(2), SOPh, and SO2Ph) at the C-1-position.

  DOI：

  10.1021/jo0488614
• 作为产物：
  描述：

  6-(tert-butyldimethylsiloxy)hex-2-yn-1-ol 在 Lindlar's catalyst 咪唑 、 喹啉 、 氢气 、 4-甲基苯磺酸吡啶 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 12.17h， 生成 (Z)-6-(tert-butyldiphenylsiloxy)-4-penten-1-ol
  参考文献：
  名称：

  Transformation of cis-Epoxy Compound to cis-2,3-Disubstituted Oxane and Investigation on Propagation Step in the Ring-Expansion Reactions of cis,trans-Diepoxy Systems

  摘要：

  Conversion of cis-epoxy compounds by successive ring-expansion reaction into trans-fused cyclic ethers was examined from both the initiation step and the propagation step. The ring-expansion reaction of cis-4,5-epoxy compounds containing a leaving group on C-1 was attempted as a unit process for the successive reaction. When a chloromesyl group was used as a leaving group, the ring expansion proceeded to give an oxane derivative (endo-type product) preferentially. On the other hand, investigation of the propagation step was carried out with respect to epoxy oxane derivatives. It was clarified that the ring-expansion reaction of cis-2,3-disubstituted oxane derivatives provided spiro acetals as products, not the desired trans-fused cyclic ethers, owing to the reaction pathway triggered by 1,2-hydride rearrangement. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00622-0

文献信息

• Use of the transannular Diels–Alder (TADA) reaction to probe biological receptors: Rational design and synthesis of tricyclic TADA adducts capable of rigidly holding pharmacophore parts
  作者：Yves A Chantigny、Yves L Dory、András Toró、Pierre Deslongchamps

  DOI：10.1139/v02-064

  日期：2002.8.1

  Transannular Diels–Alder (TADA) adducts constitute a collection of rigid structures, whose conformational diversity is rich. It is possible to design such specifically functionalized molecules capable of binding to known biological targets by molecular modelling MCSS–HOOK (multiple copy simultaneous search). Here we show that such carefully designed compounds can be easily built from small synthons. TADA adducts are very interesting due to their huge conformational diversity, their rigidity (biological interest), and their ease of synthesis (chemical interest).Key words: tricycles, synthesis, transannular Diels–Alder, macrocyclization, conformation, diversity.

  横向二烯-阿尔德（TADA）加合物构成了一系列刚性结构，其构象多样性丰富。通过分子建模MCSS-HOOK（多重拷贝同时搜索），可以设计出能够结合已知生物靶点的特定功能化分子。在这里，我们展示了这样精心设计的化合物可以很容易地由小合成子构建。TADA加合物非常有趣，因为它们具有巨大的构象多样性、刚性（生物学上的兴趣）和易于合成（化学上的兴趣）。关键词：三环、合成、横向二烯-阿尔德、大环化、构象、多样性。
• Catalytic Enantioselective Radical Cyclization via Regiodivergent Epoxide Opening
  作者：Andreas Gansäuer、Lei Shi、Matthias Otte

  DOI：10.1021/ja105023y

  日期：2010.9.1

  A catalytic enantio- and diastereoselective radical cyclization using a regiodivergent epoxide opening (REO) for radical generation is described. It is demonstrated for the first time that the diastereoselectivity of cyclizations of acyclic radicals can be controlled catalytically. Building blocks for important applications in stereoselective synthesis are readily accessed.

  描述了使用区域发散环氧化物开环 (REO) 进行自由基生成的催化对映和非对映选择性自由基环化。首次证明无环自由基环化的非对映选择性可以通过催化控制。很容易获得立体选择性合成中重要应用的构建模块。
• Transformation of cis-Epoxy Compound to cis-2,3-Disubstituted Oxane and Investigation on Propagation Step in the Ring-Expansion Reactions of cis,trans-Diepoxy Systems
  作者：Nobuyuki Hayashi、Hiroko Noguchi、Sadao Tsuboi

  DOI：10.1016/s0040-4020(00)00622-0

  日期：2000.9

  Conversion of cis-epoxy compounds by successive ring-expansion reaction into trans-fused cyclic ethers was examined from both the initiation step and the propagation step. The ring-expansion reaction of cis-4,5-epoxy compounds containing a leaving group on C-1 was attempted as a unit process for the successive reaction. When a chloromesyl group was used as a leaving group, the ring expansion proceeded to give an oxane derivative (endo-type product) preferentially. On the other hand, investigation of the propagation step was carried out with respect to epoxy oxane derivatives. It was clarified that the ring-expansion reaction of cis-2,3-disubstituted oxane derivatives provided spiro acetals as products, not the desired trans-fused cyclic ethers, owing to the reaction pathway triggered by 1,2-hydride rearrangement. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Base-Catalyzed Endo-Mode Cyclization of Allenes:  Easy Preparation of Five- to Nine-Membered Oxacycles
  作者：Chisato Mukai、Masaru Ohta、Haruhisa Yamashita、Shinji Kitagaki

  DOI：10.1021/jo0488614

  日期：2004.10.1

  A reliable and efficient procedure for constructing five- to eight-membered oxacycles has been developed. Allenes with both a phosphoryl group and a suitable delta-hydroxyalkyl side chain at the Cl-position underwent an endo mode ring-closing reaction to give five- to seven-membered oxacycles. Changing the phosphoryl group to a phosphono functionality facilitated the preparation of eight-membered congeners. Introduction of a cis double bond to the alkyl side chain of the starting allenes made possible the easy formation of medium-sized oxacycles, such as the dihydrooxocin and tetrahydrooxonin frameworks, regardless of the electron-withdrawing group (POPh2, PO(OEt)(2), SOPh, and SO2Ph) at the C-1-position.