2-Butynyl phenylacetate | 144713-04-2

• 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: 2-Butynyl phenylacetate
• 英文别名: But-2-ynyl 2-phenylacetate
• CAS: 144713-04-2
• 化学式: C₁₂H₁₂O₂
• 分子量: 188.226
• InChiKey: CIQXDTCVADWYGB-UHFFFAOYSA-N

物化性质

• 沸点：
  292.6±23.0 °C(Predicted)
• 密度：
  1.075±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  2-Butynyl phenylacetate 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 以80%的产率得到2-butynyl 2-diazophenylacetate
  参考文献：
  名称：

  金催化的炔丙基重氮乙酸盐的1,2-酰氧基迁移/偶联级联：异霉素衍生物的合成

  摘要：

  已经开发了一种有效的金（I）催化的碳环化反应，用于从炔丙基重氮乙酸酯合成异霉素衍生物。建议的环化途径描绘了从金（I）催化的1,2-酰氧基迁移原位生成的乙烯基金类类胡萝卜素物质的第一个例子，并通过交叉偶联反应与其余的拴系重氮官能团截获。质子添加剂的使用对于通过微调金（I）配合物的催化偏好来调节反应结果至关重要。

  DOI：

  10.1021/acs.orglett.9b00392
• 作为产物：
  描述：

  2-丁炔-1-醇 、 苯乙酰氯 反应 0.25h， 以95%的产率得到2-Butynyl phenylacetate
  参考文献：
  名称：

  Spectroscopy and Photochemistry of Phenylacetic Acid Esters and Related Substrates. The Stereoelectronic Dependence of the Aryl/Carboxyl Bichromophore Interaction

  摘要：

  The 254-nm-initiated Norrish Type II photofragmentation of the ethoxyethyl esters of a series of phenylacetic acids (1b-4b) has been studied in order to further elaborate the aryl/ester interaction that is photochemically and photophysically evident in these systems. The ethoxyethyl ester of benzonorbornene-1-carboxylic acid (5) has also been prepared and studied, as has a rigid tricyclic lactone (6) which places the chromophores in an optimal stereoelectronic relationship for interaction. The experimental work is accompanied by Hartree-Fock (HF), Natural Bond Orbital (NBO), and Configuration Interaction with Single Excitations (CIS) calculations on the methyl esters of phenylacetic acid (1a) and alpha-methoxyphenylacetic acid (4a). The calculations confirm extensive through-space (TS) and through-bond (TB) interactions between the aryl and ester pi* orbitals but fail to provide conformational or electronic arguments to explain the unusually high reactivity of the alpha-methoxy series.

  DOI：

  10.1021/jo00089a025

文献信息

• Gold(I)-Catalyzed and H₂O-Mediated Carbene Cascade Reaction of Propargyl Diazoacetates: Furan Synthesis and Mechanistic Insights
  作者：Ming Bao、Yu Qian、Han Su、Bing Wu、Lihua Qiu、Wenhao Hu、Xinfang Xu

  DOI：10.1021/acs.orglett.8b02251

  日期：2018.9.7

  A novel gold-catalyzed water-mediated carbene cascade reaction of propargyl diazoacetates has been developed. Mechanistic investigation indicates that this reaction is initiated by gold-catalyzed gold–carbene formation followed by an unprecedented 6-endo-dig carbocyclization with tethered alkyne through an oxonium ylide intermediate, terminated by a β-H elimination/protodeauration process to give the

  已开发出一种新型的金催化的炔丙基重氮乙酸酯水介导的卡宾级联反应。机理研究表明，该反应是由金催化的金卡宾的形成引发的，然后是空前的6-内消旋碳环化，通过氧代叶立德中间体与束缚的炔烃结合，然后被β-H消除/原脱氮过程终止，得到芳构化的呋喃产品具有良好的高收率和广泛的基材通用性。值得注意的是，拟议的金卡宾中间体已通过拦截实验得到了验证。
• Regio- and Stereoselective Synthesis of Fluoroalkenes by Directed Au(I) Catalysis
  作者：Benjamin C. Gorske、Curren T. Mbofana、Scott J. Miller

  DOI：10.1021/ol9016782

  日期：2009.10.1

  Au-catalyzed hydrofluorination reactions of a range of functionalized alkynes are reported. In the presence of an appropriate directing group, localized with particular spacing from the pendant alkyne, regioselective and predictable conversion of the alkyne to the Z-vinyl fluoride may be achieved, In selected cases, yields and selectivities are excellent. Additional experiments with two directing groups installed have established some initial principles with respect to a hierarchy of directing groups and their capacity for influencing hydrofluorination regioselectivity.
• Rhodium(II)-catalyzed cyclization of 2-alkynyl 2-diazo-3-oxobutanoates as a method for synthesizing substituted furans
  作者：Albert Padwa、Frederick R. Kinder

  DOI：10.1021/jo00053a009

  日期：1993.1

  A series of 2-alkynyl 2-diazo-3-oxobutanoates, when treated with a catalytic quantity of rhodium(II) acetate, were found to produce furo[3,4-c]furans in good yield. The reaction proceeds by addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to give a vinyl carbenoid which subsequently cyclizes onto the neighboring carbonyl group to produce the furan ring. In a similar manner, indeno[1,2-c]furans were produced from 2-butynyl 2-diazoarylacetates. Compounds substituted with methyl groups on the propargylic carbon atom cyclized at a slower rate. This rate diminution is attributed to the fact that the unsubstituted propargyl group can more easily achieve the required conformation for cyclization. C-H insertion was found to compete with furan formation when an alkyl group was attached to the keto functionality of the starting diazo acetoacetate. Diazo alkynyl sulfones undergo a novel oxygen transfer reaction when treated with rhodium(II) acetate at 80-degrees-C. The cyclized product is formed by sulfone oxygen attack onto the vinyl carbenoid producing a dipolar species which subsequently collapses to give the butenolide sulfoxide.
• Kasper Annette M., Nash John J., Morrison Harry, J. Org. Chem, 59 (1994) N 10, S 2792-2798
  作者：Kasper Annette M., Nash John J., Morrison Harry

  DOI：——

  日期：——
• Gold-Catalyzed 1,2-Acyloxy Migration/Coupling Cascade of Propargyl Diazoacetates: Synthesis of Isomycin Derivatives
  作者：Ming Bao、Xin Wang、Lihua Qiu、Wenhao Hu、Philip Wai Hong Chan、Xinfang Xu

  DOI：10.1021/acs.orglett.9b00392

  日期：2019.3.15

  An efficient gold(I)-catalyzed carbocyclization reaction for the synthesis of isomycin derivatives from propargyl diazoacetates has been developed. The suggested cyclization pathway delineated the first example of a vinyl gold carbenoid species generated in situ from gold(I)-catalyzed 1,2-acyloxy migration and intercepted by a cross-coupling reaction with the remaining tethered diazo functionality

  已经开发了一种有效的金（I）催化的碳环化反应，用于从炔丙基重氮乙酸酯合成异霉素衍生物。建议的环化途径描绘了从金（I）催化的1,2-酰氧基迁移原位生成的乙烯基金类类胡萝卜素物质的第一个例子，并通过交叉偶联反应与其余的拴系重氮官能团截获。质子添加剂的使用对于通过微调金（I）配合物的催化偏好来调节反应结果至关重要。