O-triisopropylsilyl-4-pentynoate | 214214-55-8

• 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: O-triisopropylsilyl-4-pentynoate
• 英文别名: triisopropylsilyl pent-4-ynoate；Tri(propan-2-yl)silyl pent-4-ynoate
• CAS: 214214-55-8
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: PLVXEMJBGOGOAT-UHFFFAOYSA-N

物化性质

• 沸点：
  272.7±23.0 °C(Predicted)
• 密度：
  0.896±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.12
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  O-triisopropylsilyl-4-pentynoate 在 咪唑 、 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 41.17h， 生成 (R)-methyl 7-((tert-butyldiphenylsilyl)oxy)-8-((4-methoxybenzyl)oxy)oct-4-ynoate
  参考文献：
  名称：

  通过钯催化不对称烯丙基环化Stereodivergent策略Neurofuran合成：7-全合成外延-ST-Δ 8 -10- Neurofuran

  摘要：

  神经呋喃是由于氧化应激增加而在人脑中体内形成的，它们可能是神经元氧化应激的重要生物标志物。在本文中，从单一的非手性前体中消旋二醇11开始，开发了一种对映体选择性立体发散方法，用于两种主要的AC和ST类神经呋喃。通过分别使用（S，S）-L1和（R，R）-L2配体的Pd催化的不对称烯丙基烷基化来确保THF核的绝对构型。

  DOI：

  10.1021/jo4004647
• 作为产物：
  描述：

  三异丙基氯硅烷 、 炔丙基脲 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 O-triisopropylsilyl-4-pentynoate
  参考文献：
  名称：

  Tandem Zirconocene Homologation−Aldimine Allylation

  摘要：

  [GRAPHICS]Hydrozirconation of internal and terminal alkynes followed by in situ transmetalation to dimethylzinc and treatment with diiodomethane leads to chain extended allylic organometallics. Addition to N-phosphinoyl or N-sulfonyl aldimines provides homoallylic amines in 48-87% yield and 3:2 to > 20:1 diastereomeric ratios favoring ant products.

  DOI：

  10.1021/ol0163880

文献信息

• A Simple and Versatile Re-Catalyzed Meyer-Schuster Rearrangement of Propargylic Alcohols to α,β-Unsaturated Carbonyl Compounds
  作者：Massimo Stefanoni、Marco Luparia、Alessio Porta、Giuseppe Zanoni、Giovanni Vidari

  DOI：10.1002/chem.200802622

  日期：2009.4.14

  Rhenium does the job! A readily available rhenium complex efficiently catalyzed the direct Meyer–Schuster‐like rearrangement of different alkyl‐ and aryl‐substituted propargylic secondary and tertiary alcohols to the corresponding α,β‐unsaturated compounds, which were produced with virtually complete E stereoselectivity. The reaction proceeded under neutral conditions and no racemization of potentially

  hen胜任！易于获得的rh络合物有效地催化了不同的烷基和芳基取代的炔丙基仲和叔醇的直接Meyer-Schuster式重排，生成了相应的α，β-不饱和化合物，这些化合物实际上具有完全的E立体选择性。反应在中性条件下进行，未观察到外消旋的潜在可烯化的立体中心。
• Dimethylzinc-Mediated Additions of Alkenylzirconocenes to Aldimines. New Methodologies for Allylic Amine and <i>C</i>-Cyclopropylalkylamine Syntheses
  作者：Peter Wipf、Christopher Kendall、Corey R. J. Stephenson

  DOI：10.1021/ja028092a

  日期：2003.1.1

  Hydrozirconation of alkynes with zirconocene hydrochloride followed by in situ transmetalation to dimethylzinc provides access to reactive alkenyl organometallic reagents from readily available precursors. Upon addition of imines, 1,2-attack leads to synthetically useful allylic amine building blocks. In the presence of CH2I2 or CH2Cl2, the N-metalated allylic amide intermediate is cyclopropanated and C-cyclopropylalkylamines are formed in high yield and excellent diastereoselectivities favoring the anti products. The use of enynes as starting materials for this domino reaction provides conjugated biscyclopropanes and thus allows the stereoselective formation of five new carbon-carbon bonds. A transition state that explains the need for both zirconocene complex and alkyl zinc in the cyclopropanation reaction is proposed.
• Transition-Metal-Mediated Cascade Reactions:  <i>C</i>,<i>C</i>-Dicyclopropylmethylamines by Way of Double C,C-σ-Bond Insertion into Bicyclobutanes
  作者：Peter Wipf、Corey R. J. Stephenson、Kazuo Okumura

  DOI：10.1021/ja038623a

  日期：2003.12.1

  The organometallic multicomponent reaction of alkenyl zirconocene, alkynyl imine, and zinc carbenoid in the presence of dimethylzinc leads to novel C,C-dicyclopropylmethylamines. The formation of intermediate bicyclo[1.1.0]butanes represents the first synthetically useful example of a double C,C-sigma-bond insertion, and the increase in structural complexity from starting materials is highlighted by the formation of nine new C,C-bonds in the final product.
• Zirconocene−Zinc Transmetalation and in Situ Catalytic Asymmetric Addition to Aldehydes
  作者：Peter Wipf、Seth Ribe

  DOI：10.1021/jo9811827

  日期：1998.9.1
• Dimethylzinc-Mediated Addition of Alkenylzirconocenes to α-Keto and α-Imino Esters
  作者：Peter Wipf、Corey R. J. Stephenson

  DOI：10.1021/ol0347141

  日期：2003.7.1

  graphicHydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivitles.