carbonic acid 1,1-dimethyl-3-p-tolyl-prop-2-ynyl ester methyl ester | 952527-70-7

• 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: carbonic acid 1,1-dimethyl-3-p-tolyl-prop-2-ynyl ester methyl ester
• 英文别名: methyl (2-methyl-4-(p-tolyl)but-3-yn-2-yl) carbonate；methyl 2-methyl-4-(4-methylphenyl)but-3-yn-2-yl carbonate；methyl [2-methyl-4-(4-methylphenyl)but-3-yn-2-yl] carbonate
• CAS: 952527-70-7
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: CIYKDDKAGPRXKM-UHFFFAOYSA-N

物化性质

• 沸点：
  310.8±35.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.91
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  carbonic acid 1,1-dimethyl-3-p-tolyl-prop-2-ynyl ester methyl ester 在 四(三苯基膦)钯 zinc trifluoromethanesulfonate 作用下， 以 四氢呋喃 、 水 、 苯 为溶剂， 反应 48.0h， 生成 3-isopropenyl-1-(4-nitro-phenyl)-4-p-tolyl-pyrrole-2,5-dione
  参考文献：
  名称：

  Efficient Synthesis of Maleimides and Carbazoles via Zn(OTf)₂-Catalyzed Tandem Annulations of Isonitriles and Allenic Esters

  摘要：

  Lewis acid Zn(OTf)(2)-catalyzed tandem annulations of isonitriles and allenic esters which lead to efficient and flexible syntheses of a range of biologically significant maleimides and carbazoles and related compounds are reported. A mechanistic rationale is proposed to account for the observed reactivity.

  DOI：

  10.1021/ol7018086
• 作为产物：
  描述：

  2-甲基-3-丁炔-2-醇 在 palladium diacetate copper(l) iodide 、 sodium hydride 、 二乙胺 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 61.0h， 生成 carbonic acid 1,1-dimethyl-3-p-tolyl-prop-2-ynyl ester methyl ester
  参考文献：
  名称：

  Efficient Synthesis of Maleimides and Carbazoles via Zn(OTf)₂-Catalyzed Tandem Annulations of Isonitriles and Allenic Esters

  摘要：

  Lewis acid Zn(OTf)(2)-catalyzed tandem annulations of isonitriles and allenic esters which lead to efficient and flexible syntheses of a range of biologically significant maleimides and carbazoles and related compounds are reported. A mechanistic rationale is proposed to account for the observed reactivity.

  DOI：

  10.1021/ol7018086

文献信息

• Umpolung coupling of pyridine-2-carboxaldehydes and propargylic carbonates <i>via</i> N-heterocyclic carbene/palladium synergetic catalysis
  作者：Weiyang Bi、Yunhui Yang、Song Ye、Congyang Wang

  DOI：10.1039/d1cc01311d

  日期：——

  reaction of pyridine-2-carboxaldehydes and propargylic carbonates has been developed for the first time through N-heterocyclic carbene/palladium cooperative catalysis with the judicious selection of the palladium catalyst, ligand and N-heterocyclic carbene, giving the propargylic ketones regioselectively.

  吡啶-2-羧醛与碳酸丙炔酯的umpolung交叉偶联反应是通过N-杂环卡宾/钯的协同催化以及明智地选择钯催化剂，配体和N-杂环卡宾而首次开发的，从而得到了炔丙基酮区域选择性。
• Domino C–H Activation/Directing Group Migration/Alkyne Annulation: Unique Selectivity by d⁶-Cobalt(III) Catalysts
  作者：Cuiju Zhu、Rositha Kuniyil、Becky B. Jei、Lutz Ackermann

  DOI：10.1021/acscatal.9b05413

  日期：2020.4.3

  control in Cp*CoIII-catalyzed domino C–H activation/pyridine directing group migration/alkyne annulation has been accomplished through the nucleophilicity of an organometallic cobalt intermediate with a d6 electron configuration. Detailed mechanistic studies provided compelling evidence for a facile C–H activation along with a favorable migration of the directing group for the Cp*CoIII catalysis, rather

  通过具有ad 6电子构型的有机金属钴中间体的亲核性，完成了Cp * Co III催化的多米诺骨牌CH-H活化/吡啶引导基团迁移/炔烃环化反应中的不同选择性控制。详细的机理研究提供了令人信服的证据，证明了C–H的活化很容易，并且Cp * Co III催化的导向基团有良好的迁移，而不是（CO）3 Mn I歧管观察到的β-氧消除。
• Ag(I)-Catalyzed Nucleophilic Addition and Friedel–Crafts Alkylation between α-Oxoketene Dithioacetals and Propargyl Carbonates
  作者：Manman Wang、Dachang Bai、Lingheng Kong、Bingxian Liu、Xingwei Li

  DOI：10.1021/acs.orglett.8b03180

  日期：2018.12.21

  Silver-catalyzed nucleophilic addition and intramolecular Friedel–Crafts alkylation between α-oxoketene dithioacetals and tertiary propargylic carbonates have been realized. The reactions proceeded in moderate to good yields with broad substrate scope, providing a straightforward method for the synthesis of substituted indenes.

  已经实现了银催化的亲核加成以及α-氧杂环丁烯二硫缩醛与叔碳酸炔丙酯之间的分子内Friedel-Crafts烷基化反应。反应以中等至良好的收率进行，具有广泛的底物范围，为合成取代的茚提供了直接的方法。
• Mn‐Catalyzed Dehydrocyanative Transannulation of Heteroarenes and Propargyl Carbonates through C−H Activation: Beyond the Permanent Directing Effects of Pyridines/Pyrimidines
  作者：Guangfan Zheng、Jiaqiong Sun、Youwei Xu、Shuailei Zhai、Xingwei Li

  DOI：10.1002/anie.201900166

  日期：2019.4

  Pyridines/pyrimidines are common and effective directing groups in C−H activation. However, they are poorly functionalizable heteroarenes. Reported in this work is Mn‐catalyzed dehydrocyanative transannulation between three classes of heteroarenes and propargyl carbonates. The pyridyl/pyrimidyl groups in the heteroarenes initially function as directing groups to enable C−H allenylation; they then undergo

  吡啶/嘧啶是CH活化中常见的有效引导基团。但是，它们是功能差的杂芳烃。这项工作报告的是三类杂芳烃和碳酸炔丙酯之间的锰催化脱氢氰基转移环。杂芳烃中的吡啶基/嘧啶基最初起使CH烯丙基化的引导基团的作用。然后，它们与烯丙基部分进行分子内Diels–Alder / retroDiels–Alder反应，生成稠合的碳/杂环。分离了反应不同阶段的三个关键中间体。
• Manganese(I)-Catalyzed Synthesis of Fused Eight- and Four-Membered Carbocycles via C–H Activation and Pericyclic Reactions
  作者：Youwei Xu、Guangfan Zheng、Lingheng Kong、Xingwei Li

  DOI：10.1021/acs.orglett.9b01139

  日期：2019.5.3

  facile construction of complex cycles. On the other hand, metal-catalyzed C–H activation has been established as an important strategy for rapid synthesis of complex structures. The two areas are integrated in Mn(I)-catalyzed redox-neutral coupling of 3-alkenyl- and 3-allylindoles with propargylic carbonates, which occurred via C–H allenylation with subsequent pericyclic reactions to afford fused eight-

  周环反应使得可以容易地构建复杂的循环。另一方面，金属催化的C–H活化已被确立为快速合成复杂结构的重要策略。这两个区域都整合在了Mn（I）催化的3-烯基和3-烯丙醇的氧化还原-中性偶合与炔丙基碳酸酯中，这是通过C-H烯基化和随后的周环反应发生的，从而得到稠合的八元和四元碳环， 分别。