2-(1,2-dihydro-naphthalen-2-yl)-2-methyl-propionic acid methyl ester

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-(1,2-dihydro-naphthalen-2-yl)-2-methyl-propionic acid methyl ester
• 英文别名: 2-(1,2-dihydronaphthalen-2-yl)-2-methylpropionic acid methyl ester；methyl-2-(1,2-dihydronaphthalen-2-yl)-2-methylpropanoate；Methyl 2-(1,2-dihydronaphthalen-2-yl)-2-methylpropanoate
• 化学式: C₁₅H₁₈O₂
• 分子量: 230.307
• InChiKey: UWGOHMKPFLDNFO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(1,2-dihydro-naphthalen-2-yl)-2-methyl-propionic acid methyl ester 在 sodium hydroxide 、 N-甲基咪唑 、 碳酸氢钠 、 potassium iodide 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 9-iodo-3,3-dimethyl-3a,4,9,9a-tetrahydronaphtho[2,3-b]-furan-2(3H)-one
  参考文献：
  名称：

  Synthesis of 2-Substituted 1,2-Dihydronaphthalenes and 1,2-Dihydroanthracenes Using a Recyclable Molybdenum Dearomatization Agent

  摘要：

  Polycyclic aromatic hydrocarbons (PAHs; e.g., naphthalene and anthracene) form stable eta(2)-bound complexes with the dearomatizing fragment {TpMo(NO)(MeIm)} (where Tp = hydridotris(pyrazolyl)borate; MeIm = 1-methylimidazole). These complexes undergo protonation at the alpha carbon followed by regioselective nucleophilic addition at the adjacent beta carbon. The nucleophile (a pyrrole or an enolate) adds stereoselectively, anti to the face of metal coordination. The resulting 1,2-dihydroarene ligand may be isolated via metal oxidation by iodine to provide the free 1,2-dihydroarene in moderate yield (similar to 60%), as well as TpMo(NO)(MeIm)(I), the precursor of the original PAH complex (similar to 80-90%). Thus, a formal catalytic cycle for the dearomatization of naphthalene and anthracene has been demonstrated.

  DOI：

  10.1021/acs.organomet.5b00509
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 以 乙腈 为溶剂， 反应 1.0h， 以34 mg的产率得到2-(1,2-dihydro-naphthalen-2-yl)-2-methyl-propionic acid methyl ester
  参考文献：
  名称：

  Binding and Activation of Aromatic Molecules by a Molybdenum π-Base

  摘要：

  Compounds having the form TpMo(NO)(1-methylimidazole)(eta(2)-L(pi)) (Tp = hydridotris(pyrazolyl)borate; L(pi) = cyclohexene, naphthalene, furan, thiophene, and acetone) were synthesized in 31-41% yield by the reduction of TpMo(NO)Br(2) in the presence of 1-methylimidazole and the respective pi-acidic organic ligand. The structure of the naphthalene complex was confirmed by single-crystal X-ray diffraction. Degradation studies showed the bound aromatics to have half-lives of 37-236 h in acetone solution at 20 degrees C. A tandem addition across the bound ring of the naphthalene complex yielded a free 1,2-dihydronaphthalene in 80% yield following decomplexation.

  DOI：

  10.1021/ja021057j

文献信息

• 4-(Dimethylamino)pyridine (DMAP) as an Acid-Modulated Donor Ligand for PAH Dearomatization
  作者：Jeffery T. Myers、Steven J. Dakermanji、Timothy R. Chastanet、Philip J. Shivokevich、Laura J. Strausberg、Michal Sabat、William H. Myers、W. Dean Harman

  DOI：10.1021/acs.organomet.6b00780

  日期：2017.2.13

  The dearomatization of naphthalene and anthracene is explored by their eta(2) coordination to TpMo(NO)(MeIm)} and TpMo(NO)(DMAP)} (where Tp = hydridotris(pyrazolyl)borate, MeIm = 1-methylimidazole, and DMAP = 4-(dimethylamino)pyridine). The DMAP and MeIm complexes have nearly identical redox properties and abilities to bind these polycyclic aromatic hydrocarbons (PAHs), but unlike MeIm, the DMAP ligand can be protonated at N while remaining bound to the metal. This action enhances the pi- acidic properties of DMAP, resulting in greater stability of the molybdenum toward oxidation by acid. Utilizing this feature of.the DMAP ligand, several new 1,2-dihydronaphthalenes and 1,2-dihydroanthracenes were prepared. Furthermore, it was found that acetals and Michael acceptors could function as electrophiles for the PAHs using the DMAP system, resulting in several new mono- and 1,4-dialkylated products.
• Ligand-Modulated Stereo- and Regioselective Tandem Addition Reactions of Rhenium-Bound Naphthalene
  作者：Mark T. Valahovic、T. Brent Gunnoe、Michal Sabat、W. Dean Harman

  DOI：10.1021/ja012066f

  日期：2002.4.1

  A series of complexes of the form TpRe(CO)(L)(eta(2)-naphthalene) (Tp = hydridotris(pyrazolyl)borate) undergoes tandem electrophile/nucleophile addition reactions with a high degree of regiocontrol depending on the auxiliary ligand, L. When L = PMe3, the reaction of the eta(2)-naphthalene complex with triflic acid followed by a silyl ketene acetal favors the 1,4-addition product, whereas when L = pyridine, N,N-dimethylaminopyridine, N-methylimidazole, or NH3 the 1,2-addition product is favored. These reactions proceed with excellent stereocontrol: both electrophile (H+, D+) and nucleophile (silyl ketene acetal) add anti to the face of metal coordination, and a single coordination diastereomer can be isolated for each reaction. one-electron oxidation of the Re complex affords the corresponding free dihydronaphthalene in good yield.
• Binding and Activation of Aromatic Molecules by a Molybdenum π-Base
  作者：Scott H. Meiere、Joseph M. Keane、T. Brent Gunnoe、Michal Sabat、W. Dean Harman

  DOI：10.1021/ja021057j

  日期：2003.2.1

  Compounds having the form TpMo(NO)(1-methylimidazole)(eta(2)-L(pi)) (Tp = hydridotris(pyrazolyl)borate; L(pi) = cyclohexene, naphthalene, furan, thiophene, and acetone) were synthesized in 31-41% yield by the reduction of TpMo(NO)Br(2) in the presence of 1-methylimidazole and the respective pi-acidic organic ligand. The structure of the naphthalene complex was confirmed by single-crystal X-ray diffraction. Degradation studies showed the bound aromatics to have half-lives of 37-236 h in acetone solution at 20 degrees C. A tandem addition across the bound ring of the naphthalene complex yielded a free 1,2-dihydronaphthalene in 80% yield following decomplexation.
• Synthesis of 2-Substituted 1,2-Dihydronaphthalenes and 1,2-Dihydroanthracenes Using a Recyclable Molybdenum Dearomatization Agent
  作者：Jeffery T. Myers、Philip J. Shivokevich、Jared A. Pienkos、Michal Sabat、William H. Myers、W. Dean Harman

  DOI：10.1021/acs.organomet.5b00509

  日期：2015.7.27

  Polycyclic aromatic hydrocarbons (PAHs; e.g., naphthalene and anthracene) form stable eta(2)-bound complexes with the dearomatizing fragment TpMo(NO)(MeIm)} (where Tp = hydridotris(pyrazolyl)borate; MeIm = 1-methylimidazole). These complexes undergo protonation at the alpha carbon followed by regioselective nucleophilic addition at the adjacent beta carbon. The nucleophile (a pyrrole or an enolate) adds stereoselectively, anti to the face of metal coordination. The resulting 1,2-dihydroarene ligand may be isolated via metal oxidation by iodine to provide the free 1,2-dihydroarene in moderate yield (similar to 60%), as well as TpMo(NO)(MeIm)(I), the precursor of the original PAH complex (similar to 80-90%). Thus, a formal catalytic cycle for the dearomatization of naphthalene and anthracene has been demonstrated.