2-butynyl 2-diazophenylacetate | 132353-11-8

• 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 2-diazophenylacetate
• 英文别名: but-2-ynyl 2-diazo-2-phenylacetate；but-2-yn-1-yl 2-diazo-2-phenylacetate；But-2-ynyl 2-diazo-2-phenylacetate
• CAS: 132353-11-8
• 化学式: C₁₂H₁₀N₂O₂
• 分子量: 214.224
• InChiKey: DJJZGHXTZMQXDT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-butynyl 2-diazophenylacetate 在 甲醇 、 Ph₃PAuNTf₂ 、 水 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 9.0h， 以78%的产率得到4-methyl-5-methylene-3-phenylfuran-2(5H)-one
  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-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

文献信息

• Chemodivergent Synthesis of Oxazoles and Oxime Ethers Initiated by Selective C–N/C–O Formation of Oximes and Diazo Esters
  作者：Zhenjie Qi、Shaozhong Wang

  DOI：10.1021/acs.orglett.1c03252

  日期：2021.11.5

  Chemodivergent reactions of oximes and diazo esters involving Rh-catalyzed [3+2] annulation and photodriven O–H insertion have been developed to generate oxazoles and oxime ethers. A range of aldehyde and ketone oximes reacted with α-diazocarbonyl compounds in a controllable manner in which functional groups, including ketone, ester, amide, ether, thiol ether, silane, alkene, allene, and alkyne groups

  已经开发了涉及 Rh 催化的 [3+2] 环化和光驱动 O-H 插入的肟和重氮酯的化学发散反应，以生成恶唑和肟醚。一系列醛和酮肟以可控方式与 α-重氮羰基化合物反应，其中包括酮、酯、酰胺、醚、硫醇醚、硅烷、烯烃、丙二烯和炔基在内的官能团具有良好的耐受性。
• 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。
• Electrosynthesis of Stabilized Diazo Compounds from Hydrazones
  作者：Nour Tanbouza、Alessia Petti、Matthew C. Leech、Laurent Caron、Jamie M. Walsh、Kevin Lam、Thierry Ollevier

  DOI：10.1021/acs.orglett.2c01803

  日期：2022.7.1

  An electrochemical synthesis of diazo compounds from hydrazones in yields as high as 99% was performed. This method was elaborated as a useful synthetic method and demonstrated on various diazo compounds (24 examples). Apart from exhibiting an efficiency that matched that of commonly used harsh and toxic chemical oxidants, this reaction is practically simple to set up, requires mild conditions, and

  以高达 99% 的收率从腙进行了重氮化合物的电化学合成。该方法被阐述为一种有用的合成方法，并在各种重氮化合物（24 个例子）上进行了证明。除了表现出与常用的苛刻和有毒化学氧化剂相匹配的效率外，该反应实际上易于建立，需要温和的条件，并且电子效率高（3 F/mol）。
• 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.
• Preparation of oxygenated heterocycles via the cyclization reaction of α-diazo substituted alkynes
  作者：Frederick R. Kinder、Albert Padwa

  DOI：10.1016/s0040-4039(00)97184-3

  日期：1990.1