5-(2-propenyloxy)-1-pentyne | 130018-34-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-(2-propenyloxy)-1-pentyne
• 英文别名: 5-(allyloxy)-1-pentyne；5-(allyloxy)pent-1-yne；allyl 4-pentynyl ether；1-Pentyne, 5-(2-propenyloxy)-；5-prop-2-enoxypent-1-yne
• CAS: 130018-34-7
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: VQQOWEQSNADJAZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-(2-propenyloxy)-1-pentyne 在 喹哪啶酸 、 cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以94%的产率得到4-戊炔-1-醇
  参考文献：
  名称：

  CpRuIIPF6 /喹啉酸催化的化学选择性烯丙基醚裂解。一种简单实用的羟基脱保护方法。

  摘要：

  阳离子CpRu（II）配合物与奎宁酸组合显示出高反应活性和化学选择性，可催化脱保护作为烯丙基醚的羟基。该催化剂在醇溶剂中操作，不需要任何其他亲核试剂，满足了操作简便，安全和环境友好的实际要求。该脱保护策略对包括肽和核苷在内的多种多功能分子的广泛应用，可能在保护基化学中提供新的机会。[结构：见文字]

  DOI：

  10.1021/ol0493397
• 作为产物：
  描述：

  4-戊炔-1-醇 、 3-溴丙烯 在 sodium hydride 、 四丁基碘化铵 作用下， 以 四氢呋喃 、 mineral oil 、 正己烷 为溶剂， 生成 5-(2-propenyloxy)-1-pentyne
  参考文献：
  名称：

  金催化的烯丙基氧鎓叶立德重排：高效合成高度官能化的二氢呋喃-3-酮

  摘要：

  不需要“重氮”：标题反应可导致氧鎓叶立德发生重排，它是通过两种不同的机理由易于获得的均丙烯丙基烯丙基醚代替重氮化合物制备的，它们通过两种不同的机制：协同的2,3-σ重排，或逐步的1， 4烯丙基迁移，然后进行克莱森重排（请参阅方案）。

  DOI：

  10.1002/anie.201208305

文献信息

• Cross-coupling reaction of organosilicon nucleophiles
  申请人：——

  公开号：US20020183516A1

  公开（公告）日：2002-12-05

  Improved methods for generating a —C—C— bond by cross-coupling of a transferable group with an acceptor group. The transferable group is a substituent of an organosilicon nucleophile and the acceptor group is provided as an organic electrophile. The reaction is catalyzed by a Group 10 transition metal complex (e.g., Ni, Pt or Pd), particularly by a palladium complex. Certain methods of this invention use improved organosilicon nucleophiles which are readily prepared, can give high product yields and exhibit high stereo selectivity. Methods of this invention employ activating ions such as halides, hydroxide, hydride and silyloxides. In specific embodiments, organosilicon nucleophilic reagents of this invention include siloxanes, particularly cyclic siloxanes. The combination of the cross-coupling reactions of this invention with ring-closing metathesis, hydrosilylation and intramolecular hydrosilylation reactions provide useful synthetic strategies that have wide application.

  通过将可转移基团与受体基团进行交叉偶联来生成一种改进的—C—C—键的方法。可转移基团是有机硅亲核试剂的取代基，受体基团以有机亲电试剂的形式提供。该反应由第10族过渡金属配合物催化（例如，Ni、Pt或Pd），特别是钯配合物。本发明的某些方法使用改进的有机硅亲核试剂，这些试剂易于制备，可以提供高产率产物并表现出高立体选择性。本发明的方法采用活化离子，如卤化物、氢氧化物、氢化物和硅氧化物。在具体实施例中，本发明的有机硅亲核试剂包括硅氧烷，特别是环状硅氧烷。本发明的交叉偶联反应与环闭合重排、氢硅烷化和分子内氢硅烷化反应的结合提供了广泛应用的有用合成策略。
• Method of removing allyl series protecting group using novel ruthenium complex and method of synthesizing allyl ethers
  申请人：Kitamura Masato

  公开号：US20050203317A1

  公开（公告）日：2005-09-15

  A cyclopentadienyl ruthenium (II) complex or (iv) complex having an α-imino acid type ligand or an α-amino acid type ligand.

  一个具有α-亚胺酸型配体或α-氨基酸型配体的环戊二烯基钌（II）配合物或（IV）配合物。
• Concise Stereoselective Synthesis of Oxaspirocycles with 1-Tosyl-1,2,3-triazoles: Application to the Total Syntheses of (±)-Tuberostemospiroline and (±)-Stemona-lactam R
  作者：Junkai Fu、Hongjuan Shen、Yuanyuan Chang、Chuangchuang Li、Jianxian Gong、Zhen Yang

  DOI：10.1002/chem.201403756

  日期：2014.9.26

  A 4‐substituted‐1‐tosyl‐1,2,3‐triazole‐based stereoselective synthesis of structurally diverse oxaspirocycles is reported. The synthesis involves Rh‐catalyzed loss of nitrogen from 4‐substituted‐1‐tosyl‐1,2,3‐triazoles, Grignard reaction, and a ring‐closing metathesis reaction as key steps. By employing readily available and stable 4‐substituted‐1‐tosyl‐1,2,3‐triazoles as surrogates of diazo compounds

  据报道，基于4-取代-1，对甲苯基1,2,3-三唑的立体选择性合成结构多样的oxaspirocycles。合成涉及关键步骤，其中包括Rh催化的4-取代-1-甲苯磺酰基1,2,3-三唑的氮损失，格氏反应和闭环易位反应。通过使用现成的，稳定的4-取代-1-甲苯磺酰基1,2,3-三唑作为重氮化合物和氮源的替代物，获得了两种类型的氧杂螺环。后者含有相邻的氮立体中心，可以作为许多天然产物的核心结构。该化学方法已成功应用于（±）-溴代螺螺啉和（±）-stemona-lactam R的全部合成中。
• A Tandem Cyclization-Onium Ylide Rearrangement-Cycloaddition Sequence for the Synthesis of Benzo-Substituted Cyclopentenones
  作者：Albert Padwa、Jamal M. Kassir、Mark A. Semones、M. David Weingarten

  DOI：10.1021/jo00106a014

  日期：1995.1

  A new annulation sequence leading to benzo-substituted cyclopentenones is effected by treating o-alkynyl-substituted alpha-diazoacetophenones containing tethered heteroatoms with Rh(II) carboxylates. The reaction involves addition of the initially formed keto carbenoid onto the acetylenic pi-bond to give a rearranged vinyl carbenoid. Sulfonium ylide formation occurred both intra- and intermolecularly when the reaction was carried out in the presence of a sulfide. In the case where an ether oxygen was present on the backbone of the vinyl carbenoid, the resulting oxonium ylide underwent a [1,2]- or [2,3]-shift to give the rearranged product. These cyclic metallocarbenoids were also found to interact with a neighboring carbonyl or oximino pi-bond to produce carbonyl or azomethine ylides. The 1,3-dipoles generated in this manner were trapped with dimethyl acetylenedicarboxylate. The domino transformation was also performed intramolecularly by attaching a trapping agent directly to the carbonyl group. Incorporation of an amido carbonyl on the alkyne side chain was found to dramatically alter the course of the tandem annulation reaction. A novel rearranged cycloadduct was formed in high yield whose structure was elucidated by X-ray crystallography. The mechanism for its formation involves the opening of a transient intermediate oxabicyclo[2.2.1]heptane followed by a Wagner-Meerwein rearrangement.
• Highly Stereoselective Hydrocarbation of Terminal Alkynes via Pt-Catalyzed Hydrosilylation/Pd-Catalyzed Cross-Coupling Reactions
  作者：Scott E. Denmark、Zhigang Wang

  DOI：10.1021/ol0156751

  日期：2001.4.1

  [GRAPHICS]The formal addition of an aryl-H or alkenyl-H bond across a terminal alkyne has been accomplished by the combination of platinum-catalyzed hydrosilylation followed by palladium-catalyzed cross-coupling, The use of the t-Bu3P-Pt(DVDS) catalyst in combination with tetramethyldisiloxane gave excellent regio- and stereoselectivity with a number of alkyne substrates, Subsequent, fluoride-promoted cross-coupling proceeded in high yield and stereospecificity for a variety of aryl halides.