2-d3-methoxynaphthalene | 97073-37-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-d3-methoxynaphthalene
• 英文别名: Naphthalene, 2-(methoxy-d3)-；2-(trideuteriomethoxy)naphthalene
• CAS: 97073-37-5
• 化学式: C₁₁H₁₀O
• 分子量: 161.176
• InChiKey: LUZDYPLAQQGJEA-FIBGUPNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-d3-methoxynaphthalene 在 异丙基溴化镁 、 nickel diacetate 、 1,3-二环己基氯化咪唑 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 萘
  参考文献：
  名称：

  镍与烷基格氏试剂通过C–O键裂解进行的镍催化交叉偶联

  摘要：

  已经开发了镍催化的甲氧基芳烃与烷基格氏试剂的交叉偶联，这涉及到C（芳基）-OMe键的裂解。使用1，3-二环己基咪唑-2-亚烷基作为配体允许引入各种烷基，包括Me，Me 3 SiCH 2，ArCH 2，金刚烷基和环丙基。该方法还可用于带有C（芳基）–OMe键的复杂分子的烷基化修饰。

  DOI：

  10.1021/acs.orglett.5b02200
• 作为产物：
  描述：

  氘代甲醇 、 2-溴萘 在 palladium diacetate 、 caesium carbonate 、 2-二-叔丁膦基-2',4',6'-三异丙基联苯 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以86%的产率得到2-d3-methoxynaphthalene
  参考文献：
  名称：

  芳基和杂芳基卤化物的三氘代甲氧基化

  摘要：

  已经开发了直接获取三重氢甲氧基化芳香族和杂芳香族化合物的方法。通过使用由市售单齿膦配体 tBuXPhos 和 Pd(OAc)2 组成的催化剂体系，各种芳基和杂芳基卤化物在温和的反应条件下进行 d3-甲氧基化。廉价的 CD3OD 作为一种有效的三氘代甲氧基化剂。

  DOI：

  10.1002/ejoc.201200753

文献信息

• Trideuteromethylation Enabled by a Sulfoxonium Metathesis Reaction
  作者：Zuyuan Shen、Shilei Zhang、Huihui Geng、Jiarui Wang、Xinyu Zhang、Anqi Zhou、Cheng Yao、Xiaobei Chen、Wei Wang

  DOI：10.1021/acs.orglett.8b03641

  日期：2019.1.18

  A conceptually novel sulfoxonium metathesis reaction between TMSOI and cost-effective DMSO-d6 is developed for the efficient generation of a new trideuteromethylation reagent TDMSOI. The new reagent TDMSOI is produced highly efficiently by simply heating a mixture of TMSOI and DMSO-d6 and directly used for subsequent trideuteromethylation in a “one-pot” operation. The preparative power of the new versatile

  TMSOI 和经济高效的 DMSO- d 6之间的概念上新颖的硫鎓复分解反应被开发出来，用于有效生成新型三氘代甲基化试剂 TDMSOI。新试剂TDMSOI只需加热TMSOI和DMSO- d 6的混合物即可高效生产，并直接用于后续的“一锅”操作中的三氘代甲基化。新的多功能试剂和“一锅”方案的制备能力通过其以高产率和有用的方式将-CD 3部分安装到广泛的功能中而得到证明，包括苯酚、苯硫酚、酸性胺和烯醇化亚甲基单元。氘化水平 (>87% D)。
• Nickel-catalyzed reductive cleavage of aryl alkyl ethers to arenes in absence of external reductant
  作者：Mamoru Tobisu、Toshifumi Morioka、Akimichi Ohtsuki、Naoto Chatani

  DOI：10.1039/c5sc00305a

  日期：——

  The reductive cleavage of the C-O bonds of aryl ethers has numerous potential in organic synthesis. Although several catalysts that can promote the reductive cleavage of aryl ethers have been...

  芳基醚的CO键的还原裂解在有机合成中具有许多潜力。尽管已经有几种可以促进芳基醚还原裂解的催化剂...
• Nickel-Mediated Hydrogenolysis of C–O Bonds of Aryl Ethers: What Is the Source of the Hydrogen?
  作者：Paul Kelley、Sibo Lin、Guy Edouard、Michael W. Day、Theodor Agapie

  DOI：10.1021/ja300326t

  日期：2012.3.28

  ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel aryl methoxide complex. Formal β-H elimination from this species produced a nickel aryl hydride which can undergo reductive elimination in the presence of formaldehyde to generate

  用（二膦）芳基甲基醚对镍对芳基醚进行氢解的机理研究。分离出含有与芳基-O 键相邻的 Ni-芳烃相互作用的 Ni(0) 配合物。加热导致芳基-O 键活化并生成芳基甲醇镍络合物。该物种的正式β-H消除产生芳基氢化镍，其可以在甲醛存在下进行还原消除以生成Ni(0)的一氧化碳加合物。报道的配合物描绘了镍催化芳醚氢解的合理机制。对先前报道的使用同位素标记底物的催化系统的研究与化学计量系统中提出的机制一致，涉及从醇镍中消除 β-H，而不是通过 H(2) 裂解 Ni-O 键。
• Ni-Catalyzed Reduction of Inert C−O Bonds: A New Strategy for Using Aryl Ethers as Easily Removable Directing Groups
  作者：Paula Álvarez-Bercedo、Ruben Martin

  DOI：10.1021/ja106943q

  日期：2010.12.15

  An efficient Ni-catalyzed protocol for the reductive cleavage of inert C-O bonds has been developed. The method is characterized by its simplicity and wide scope, thereby allowing the use of aryl ethers as easily removable directing groups in organic synthesis.
• Combined Experimental and Theoretical Study on the Reductive Cleavage of Inert C–O Bonds with Silanes: Ruling out a Classical Ni(0)/Ni(II) Catalytic Couple and Evidence for Ni(I) Intermediates
  作者：Josep Cornella、Enrique Gómez-Bengoa、Ruben Martin

  DOI：10.1021/ja311940s

  日期：2013.2.6

  A mechanistic and computational study on the reductive cleavage of C-OMe bonds catalyzed by Ni(COD)(2)/PCy3 with silanes as reducing agents is reported herein. Specifically, we demonstrate that the mechanism for this transformation does not proceed via oxidative addition of the Ni(0) precatalyst into the C-OMe bond. In the absence of an external reducing agent, the in-situ-generated oxidative addition complexes rapidly undergo beta-hydride elimination at room temperature, ultimately leading to either Ni(0)-carbonyl- or Ni(0)-aldehyde-bound complexes. Characterization of these complexes by X-ray crystallography unambiguously suggested a different mechanistic scenario when silanes are present in the reaction media. Isotopic-labeling experiments, kinetic isotope effects, and computational studies clearly reinforced this perception. Additionally, we also found that water has a deleterious effect by deactivating the Ni catalyst via formation of a new Ni-bridged hydroxo species that was characterized by X-ray crystallography. The order in each component was determined by plotting the initial rates of the C-OMe bond cleavage at varying concentrations. These data together with the in-situ-monitoring experiments by H-1 NMR, EPR, IR spectroscopy, and theoretical calculations provided a mechanistic picture that involves Ni(I) as the key reaction intermediates, which are generated via comproportionation of initially formed Ni(II) species. This study strongly supports that a classical Ni(0)/Ni(II) for C-OMe bond cleavage is not operating, thus opening up new perspectives to be implemented in other related C-O bond-cleavage reactions.