4-cyclopropyl-2-methylbut-3-yn-2-yl methyl carbonate | 1094602-73-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: 4-cyclopropyl-2-methylbut-3-yn-2-yl methyl carbonate
• CAS: 1094602-73-9
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: MPUXSPBUZQAAMN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.96
• 重原子数：
  13.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  N-methoxy-2-phenylacrylamide 、 4-cyclopropyl-2-methylbut-3-yn-2-yl methyl carbonate 在 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 palladium on activated charcoal 、 甲酸铵 、 silver trifluoroacetate 、 lithium carbonate 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  Switchable Regioselective C−H Activation/Annulation of Acrylamides with Alkynes for the Synthesis of 2‐Pyridones

  摘要：

  A catalyst‐based switchable regioselective C−H activation/annulation of acrylamides with propargyl carbonates has been developed, delivering C5 or C6 alkenyl substituted 2‐pyridones. This robust protocol proceeds with a broad substrate scope and good functional group tolerance under redox‐neutral reaction conditions. More significantly, this reaction is highly effective with previously challenging unsymmetrical alkynes, including unbiased alkyl‐alkyl substituted alkynes, with perfect and switchable regioselectivity. Additionally, mechanistic studies and DFT calculations were performed to shed light on the switchable regioselectivity.

  DOI：

  10.1002/cssc.202400066

文献信息

• Manganese(I)‐Catalyzed C−H Activation/Diels–Alder/retro‐Diels–Alder Domino Alkyne Annulation featuring Transformable Pyridines
  作者：Cuiju Zhu、Rositha Kuniyil、Lutz Ackermann

  DOI：10.1002/anie.201900495

  日期：2019.4.8

  Complexity‐increasing Domino reactions comprising C−H allenylation, a Diels–Alder reaction, and a retro‐Diels–Alder reaction were realized by a versatile catalyst derived from earth‐abundant, non‐toxic manganese. The C−H activation/Diels–Alder/retro‐Diels–Alder alkyne annulation sequence provided step‐economical access to valuable indolone alkaloid derivatives through a facile organometallic C−H activation

  通过衍生自地球上丰富的无毒锰的多功能催化剂，实现了包括CH烯基化，Diels-Alder反应和Diels-Alder逆反应在内的增加Domino的反应。C-H活化/ Diels-Alder / retro-Diels-Alder炔烃环化序列通过简便的有机金属CH-H活化歧管和可转化的吡啶为您提供了经济实用的有价值的吲哚酮生物碱衍生物的经济途径。
• Ruthenium(II)-Catalyzed Regioselective Ortho C–H Allenylation of Electron-Rich Aniline and Phenol Derivatives
  作者：Yanni Chen、Liuyu Hu、Liuchun Liang、Fujiang Guo、Yaxi Yang、Bing Zhou

  DOI：10.1021/acs.joc.9b02787

  日期：2020.2.21

  Ortho C-H allenylation of electron-rich benzene derivatives with propargylic alcohol derivatives has been a challenge, due to their great innate tendency toward a para C-H allenylation via an SN2'-type substitution process. Here, we described a Ru(II)-catalyzed regioselective ortho C-H allenylation of electron-rich aniline and phenol derivatives, which allows the previously challenging synthesis of a

  富电子的苯衍生物与炔丙醇衍生物的邻位CH烯基化一直是一个挑战，因为它们有很大的先天倾向通过SN2'型取代过程进行对位CH烯基化。在这里，我们描述了富电子的苯胺和苯酚衍生物的Ru（II）催化的区域选择性邻CH烯基化，这使得以前具有挑战性的各种邻苯二甲酰基化的苯胺和苯酚衍生物的合成成为可能。更重要的是，还可以通过高效的手性转移，以​​高对映体过量的方式制备具有高度旋光活性的全取代的烯。在当前的催化体系中未观察到对CH烯基化产物，因此显示出区域选择性的完全可逆性。
• Palladium-Catalyzed Regioselective Cyclopropanating Allenylation of (2,3-Butadienyl)malonates with Propargylic Carbonates and Their Application to Synthesize Cyclopentenones
  作者：Wei Shu、Guochen Jia、Shengming Ma

  DOI：10.1021/ol802465k

  日期：2009.1.1

  An efficient and highly regioselective route to synthesize polysubstituted 1,3,4-alkatrien-2-yl cyclopropane derivatives via Pd(0)-catalyzed highly regioselective coupling cyclization of (2,3-butadienyl)malonate or bis(phenylsulfonyl)methane with propargylic carbonates was reported. The reaction proceeded smoothly under neutral conditions to afford the products in 73-96% yields. The products may be efficiently converted to cyclopentenone derivatives via a catalytic Pauson-Khand reaction under ambient conditions.