1-phenylprop-2-yn-1-yl benzoate | 178056-86-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-phenylprop-2-yn-1-yl benzoate
• 英文别名: 1-phenylprop-2-ynyl benzoate
• CAS: 178056-86-5
• 化学式: C₁₆H₁₂O₂
• 分子量: 236.27
• InChiKey: SYGXXPLBCFEOOR-UHFFFAOYSA-N

物化性质

• 沸点：
  363.9±30.0 °C(Predicted)
• 密度：
  1.149±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  1-phenylprop-2-yn-1-yl benzoate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 Rh₂[(N-(4-dodecylphenyl)sulfonyl)-(S)-prolinate]4 作用下， 以 正己烷 、 苯 为溶剂， 反应 0.67h， 生成 (3R,4R)-6-((S)-Benzoyloxy-phenyl-methyl)-4-ethoxy-3-phenyl-cyclohepta-1,5-dienecarboxylic acid methyl ester
  参考文献：
  名称：

  Metal Carbene-Promoted Sequential Transformations for the Enantioselective Synthesis of Highly Functionalized Cycloheptadienes

  摘要：

  A two-step, three-component coupling of an alkyne, enol ether, and vinyl diazoester was accomplished by use of successive metal carbene-catalyzed transformations. This efficient approach to cycloheptadienes is both diastereo- and enantioselective. Kinetic resolution was accomplished on dienol ethers bearing a racemic chiral center at the propargylic position. A model is offered which explains the observed selectivity and accounts for the reactivity difference between trans- and cis-dienol ethers.

  DOI：

  10.1021/ja045173t
• 作为产物：
  描述：

  (+/-)-1-苯基-2-丙炔-1-醇 生成 1-phenylprop-2-yn-1-yl benzoate
  参考文献：
  名称：

  Preparation of Arylethynylcarbinols

  摘要：

  DOI：

  10.1021/ja01177a502

文献信息

• Gold-catalyzed reactions of propargylic esters with vinylazides for the synthesis of Z- or E-configured buta-1,3-dien-2-yl esters
  作者：Sachin Bhausaheb Wagh、Rai-Shung Liu

  DOI：10.1039/c5cc05945c

  日期：——

  Gold-catalyzed synthesis of buta-1,3-dien-2-yl esters by the reaction of propargyl esters with vinylazides is described; the reaction mechanism is postulated to involve a vinyl attack of vinylazides at alkenyl gold carbenes.

  金催化合成丁-1,3-二烯-2-基酯的方法是通过丙炔基酯与乙烯叠氮化合物反应实现的；反应机理推测涉及乙烯叠氮化合物对烯基金卡宾的乙烯攻击。
• Rhodium-catalysed synthesis of fused pyrimidine derivatives employing N-sulfonyl-1,2,3-triazoles as a 1-aza-[4C] synthon
  作者：Ze-Feng Xu、Yuehui An、Yidian Chen、Shengguo Duan

  DOI：10.1016/j.tetlet.2019.06.023

  日期：2019.7

  A new synthetic application of N-sulfonyl-1,2,3-triazoles acting as a 1-aza-[4C] synthon via the 1,2-shift reaction of an α-imine rhodium carbene was developed for the synthesis of fused pyrimidine derivatives. The high reactivity of the strained three-membered 2H-azirine ring facilitated the unusual cyclization of electron-deficient dienes with electron-deficient dienophiles. The compatibility was

  通过α-亚胺铑卡宾的1,2-转移反应，N-磺酰基-1,2,3-三唑类化合物作为1-氮杂-[4C]合成子的一种新的合成应用被开发用于熔融嘧啶的合成衍生品。应变的三元2 H-叠氮基环的高反应性促进了缺电子二烯与缺电子二烯的异常环化。兼容性很好，可以容忍常见功能。观察到优异的化学选择性，并且在卡宾铑和2 H-叠氮基之间未发生反应。产品可以转换为七元多功能1 H-1,4-二氮杂卓衍生物，说明该方案在中型N杂环合成中的潜在应用。
• Palladium-Catalyzed Ring-Opening Alkynylation of Cyclopropenones
  作者：Takanori Matsuda、Yusuke Sakurai

  DOI：10.1002/ejoc.201300220

  日期：2013.7

  N-Heterocyclic carbene–palladium catalysts are used to promote addition/ring opening of cyclopropenones with terminal alkynes. The ring-opening alkynylation affords alkenyl alkynyl ketones in good yields. For reactions with propargylic esters having an aryl or alkenyl substituent at the propargylic position, [3+2] annulation occurs exclusively to give 4-methylenecyclopentenones.

  N-杂环卡宾-钯催化剂用于促进环丙烯酮与末端炔烃的加成/开环。开环炔基化以良好的产率提供烯基炔基酮。对于与在炔丙基位置具有芳基或烯基取代基的炔丙基酯的反应，[3+2]环化仅发生以产生4-亚甲基环戊烯酮。
• Copper-Catalyzed Enantioselective Propargylic Amination of Propargylic Esters with Amines: Copper−Allenylidene Complexes as Key Intermediates
  作者：Gaku Hattori、Ken Sakata、Hiroshi Matsuzawa、Yoshiaki Tanabe、Yoshihiro Miyake、Yoshiaki Nishibayashi

  DOI：10.1021/ja1047494

  日期：2010.8.4

  and limitations of the copper-catalyzed propargylic amination of various propargylic esters with amines are presented, where optically active diphosphines such as Cl-MeO-BIPHEP and BINAP work as good chiral ligands. A variety of secondary amines are available as nucleophiles for this catalytic reaction to give the corresponding propargylic amines with a high enantioselectivity. The results of some stoichiometric

  介绍了铜催化各种炔丙酯与胺的炔丙胺化的范围和局限性，其中光学活性二膦如 Cl-MeO-BIPHEP 和 BINAP 可作为良好的手性配体。多种仲胺可用作该催化反应的亲核试剂，以产生具有高对映选择性的相应炔丙基胺。一些化学计量和催化反应的结果表明，催化胺化是通过原位形成的铜 - 亚丙叉配合物进行的，其中胺对亚丙叉配合物中的亲电子 γ-碳原子的攻击是立体选择的重要步骤。对几种对位取代炔丙乙酸酯与 N-甲基苯胺反应的相对速率常数的研究表明，铜-亚丙叉基配合物的形成参与了速率决定步骤。模型反应的密度泛函理论计算结果也支持所提出的反应途径，包括铜-亚丙叉基配合物作为关键中间体。此处介绍的催化程序为制备各种手性炔丙胺提供了一种通用且直接的方法。
• Asymmetric copper-catalyzed propargylic amination with amine hydrochloride salts
  作者：Jian Huang、Han-Han Kong、Si-Jia Li、Rui-Jin Zhang、Hao-Dong Qian、Dan-Ran Li、Jin-Yu He、Yi-Nuo Zheng、Hao Xu

  DOI：10.1039/d1cc00663k

  日期：——

  The highly enantioselective copper-catalyzed propargylic amination of propargylic esters with amine hydrochloride salts has been realized for the first time using copper salts with chiral N,N,P-ligands. This method features a broad substrate scope and wide functional group tolerance, generating propargylic amines in good to excellent yields with high enantioselectivities (up to 99% ee). The utility

  首次使用具有手性N，N，P配体的铜盐实现了炔丙基酯与胺盐酸盐的高度对映选择性的铜催化炔丙基胺化。该方法具有广泛的底物范围和宽泛的官能团耐受性，可生成具有高对映选择性（高达99％ee）的良至优收率的炔丙基胺。该方法的实用性通过市售药品的后期功能化得以证明。