methyl 2-methyl-6-phenyl-3-hexyn-2-yl carbonate | 1082069-08-6

• 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: methyl 2-methyl-6-phenyl-3-hexyn-2-yl carbonate
• 英文别名: Me2C(OCO2Me)CCCH2CH2Ph；Methyl (2-methyl-6-phenylhex-3-yn-2-yl) carbonate
• CAS: 1082069-08-6
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: KLMSJCNTWSDSFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-methyl-6-phenyl-3-hexyn-2-yl carbonate 在 甲醇 、 乙醇 、 mesitylcopper(I) 、 乙二醇 、 (S)-3,3'-二溴-1,1'-联-2-萘酚 、 三甲氧基磷 作用下， 以 甲苯 为溶剂， 反应 99.0h， 生成
  参考文献：
  名称：

  铜催化合成丙二烯基硼酸。通过炔丙基硼化反应获得空间阻碍的均炔醇和胺†

  摘要：

  三取代和四取代的丙二烯基硼酸是通过一种新的多功能铜催化方法制备的。密集官能化的丙二烯基硼酸很容易与酮和亚胺发生炔丙基硼化反应，无需任何添加剂。酮的催化不对称炔丙基硼化反应具有高立体选择性，可以合成高度对映体富集的叔均炔丙醇。该反应适用于外消旋丙二烯基硼酸的动力学拆分，得到具有相邻四元立构中心的炔烃。

  DOI：

  10.1039/c7sc05123a
• 作为产物：
  描述：

  2-methyl-6-phenylhex-3-yn-2-ol 、 氯甲酸甲酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 methyl 2-methyl-6-phenyl-3-hexyn-2-yl carbonate
  参考文献：
  名称：

  Copper(I)-Catalyzed Substitution of Propargylic Carbonates with Diboron: Selective Synthesis of Multisubstituted Allenylboronates

  摘要：

  A versatile synthetic method for the preparation of the allenylboronates, Cu(I)-catalyzed reaction of propargylic carbonates with a diboron, is described. A Cu(O-t-Bu)-Xantphos catalyst system was effective for the preparation of various allenylboron compounds, allenylboronates with different substitution patterns, those with functional groups, and an axially chiral one. The Lewis acid promoted stereoselective addition to aldehydes leading to homopropargylic alcohols showed the usefulness of the new allenylboronates.

  DOI：

  10.1021/ja806602h

文献信息

• 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。
• The synthesis of allenes by Cu(i)-catalyzed regio- and stereoselective reduction of propargylic carbonates with hydrosilanes
  作者：Chongmin Zhong、Yusuke Sasaki、Hajime Ito、Masaya Sawamura

  DOI：10.1039/b910192f

  日期：——

  Cu(I)-catalyzed anti-SN2′-type reduction of internal propargylic carbonates with hydrosilanes affords various di- and trisubstituted allenes with high regioselectivities; the reactions are compatible with functional groups and work efficiently for the synthesis of optically-active allenes.

  铜(I)催化的反SN2'型内丙炔碳酸酯与氢硅烷的还原反应可以高选择性地产生多种二取代和三取代的烯烃；该反应与功能基团兼容，并且在合成光学活性烯烃方面表现出高效性。
• General and Functional Group-Tolerable Approach to Allenylsilanes by Rhodium-Catalyzed Coupling between Propargylic Carbonates and a Silylboronate
  作者：Hirohisa Ohmiya、Hideto Ito、Masaya Sawamura

  DOI：10.1021/ol902339a

  日期：2009.12.17

  The Rh-catalyzed coupling reaction between propargylic carbonates and a silylboronate afforded allenylsilanes with different substitution patterns in high yields. The reaction tolerates a variety of functional groups in propargylic carbonates. The reaction of an optically active propargylic carbonate proceeded with excellent chirality transfer with 1,3-anti stereochemistry to give an axially chiral

  炔丙基碳酸酯和甲硅烷基硼酸酯之间的Rh催化的偶联反应以高收率提供了具有不同取代方式的烯丙基硅烷。该反应可耐受炔丙基碳酸酯中的各种官能团。旋光的碳酸炔丙酯的反应以优异的手性转移与1，3-抗立体化学进行，得到轴向手性的烯丙基硅烷。
• Iron‐Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates
  作者：Aitor Bermejo‐López、Wei‐Jun Kong、Pedro J. Tortajada、Daniels Posevins、Belén Martín‐Matute、Jan‐E. Bäckvall

  DOI：10.1002/chem.202203130

  日期：2023.1.12

  borylation of propargylic acetates. The reaction is highly efficient, occurs under mild conditions, and is easy to scale up. The reaction is stereospecific and occurs with anti-SN2‘ displacement of the acetate by boron, which allows a transfer of chirality. Several transformations including propargylation and further additions highlight the synthetic utility of this reaction.

  多取代的联烯基硼酸酯很容易通过炔丙基乙酸酯的铁催化硼酸化获得。该反应效率高，条件温和，易于放大。该反应是立体有择的，发生时乙酸盐被硼反-S N 2' 置换，从而允许手性转移。包括炔丙基化和进一步添加在内的几种转化突出了该反应的合成效用。