2-methyl-3,4-dihydronaphthalen-1-ol | 157485-33-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-methyl-3,4-dihydronaphthalen-1-ol
• 英文别名: (Z)-2-Methyl-1-tetralone enolate；2-methyl-3,4-dihydro-1-naphthol
• CAS: 157485-33-1
• 化学式: C₁₁H₁₂O
• 分子量: 160.216
• InChiKey: XFBQCKITQYVIRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-3,4-dihydronaphthalen-1-ol 在 氢氧化钾 、 (+)-<(8,8-dichlorocamphoryl)sulfonyl>oxaziridine 作用下， 生成 2-chloro-2-methyl-1-tetralone
  参考文献：
  名称：

  Chemistry of oxaziridines. 18. Synthesis and enantioselective oxidations of the [(8,8-dihalocamphoryl)sulfonyl]oxaziridines

  摘要：

  The synthesis and enantioselective oxidations of [(8,8-dihalocamphoryl)sulfonyl]oxaziridines [8,8-dichloro-1,7,7-trimethyl-2'-(phenylsulfonyl)spiro[bicyclo[2.2.1]heptane-2,3'-oxazinidine]] 13 are reported. These reagents are prepared in two steps from the (camphorylsulfonyl)imine 4 by treatment of the corresponding azaenolate with electrophilic halogen sources followed by biphasic oxidation of the resulting dihalo imine 6-9 with m-CPBA/K2CO3. Of these oxaziridines the dichloro reagent 13b, available on a multigram scale, affords the highest enantioselectivities for the asymmetric oxidation of sulfides to sulfoxides (42-74%) and for the hydroxylation of enolates (often better than 95% ee). In general the molecular recognition is predicted and explained in terms of minimization of nonbonded steric interactions the transition states. For the asymmetric oxidation of sulfides to sulfoxides, secondary electronic factors related to the polarity of the sulfide and oxaziridine also play a role. Definitive evidence for chelation of the metal enolate with the C-X bond in 13 is not found. The molecular recognition is interpreted in terms of the higher reactivity of the reagents and an active-site structure which is sterically complementary with the enolate. For the asymmetric hydroxylation of the Z- and E-enolates of propiophenone (16a), the Z-enolate exhibits much higher stereoselectivity than the E-enolate: >95% vs 22% ee.

  DOI：

  10.1021/jo00052a050
• 作为产物：
  描述：

  ethyl 2-methyl-1-oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate 在 氢氧化钾 作用下， 以 甲醇 、 水 、 乙腈 为溶剂， 反应 20.0h， 生成 2-methyl-3,4-dihydronaphthalen-1-ol
  参考文献：
  名称：

  Mechanistic Insights into the Palladium-Induced Domino Reaction Leading to Ketones from Benzyl β-Ketoesters:  First Characterization of the Enol as an Intermediate

  摘要：

  The monitoring by UV spectroscopy of the Pd-catalyzed hydrogenolysis in acetonitrile of 2-methyl-2-benzyloxycarbonyl-1-indanone and 2-methyl-2-benzyloxycarbonyl-1-tetralone showed the successive formation of corresponding beta-ketoacids and enols to deliver finally the ketones. Some factors which influence the stability of the intermediates are determined. In contrast to the above benzyl beta-ketoesters, the enol was not detected from benzyl (2-methylinden-3-yl) carbonate.

  DOI：

  10.1021/jo049464w

文献信息

• US9829792B2
  申请人：——

  公开号：US9829792B2

  公开（公告）日：2017-11-28
• Mechanistic Insights into the Palladium-Induced Domino Reaction Leading to Ketones from Benzyl β-Ketoesters:  First Characterization of the Enol as an Intermediate
  作者：Jean-François Detalle、Abdelkhalek Riahi、Vincent Steinmetz、Françoise Hénin、Jacques Muzart

  DOI：10.1021/jo049464w

  日期：2004.10.1

  The monitoring by UV spectroscopy of the Pd-catalyzed hydrogenolysis in acetonitrile of 2-methyl-2-benzyloxycarbonyl-1-indanone and 2-methyl-2-benzyloxycarbonyl-1-tetralone showed the successive formation of corresponding beta-ketoacids and enols to deliver finally the ketones. Some factors which influence the stability of the intermediates are determined. In contrast to the above benzyl beta-ketoesters, the enol was not detected from benzyl (2-methylinden-3-yl) carbonate.
• Chemistry of oxaziridines. 18. Synthesis and enantioselective oxidations of the [(8,8-dihalocamphoryl)sulfonyl]oxaziridines
  作者：Franklin A. Davis、Michael C. Weismiller、Christopher K. Murphy、R. Thimma Reddy、Band Chi Chen

  DOI：10.1021/jo00052a050

  日期：1992.12

  The synthesis and enantioselective oxidations of [(8,8-dihalocamphoryl)sulfonyl]oxaziridines [8,8-dichloro-1,7,7-trimethyl-2'-(phenylsulfonyl)spiro[bicyclo[2.2.1]heptane-2,3'-oxazinidine]] 13 are reported. These reagents are prepared in two steps from the (camphorylsulfonyl)imine 4 by treatment of the corresponding azaenolate with electrophilic halogen sources followed by biphasic oxidation of the resulting dihalo imine 6-9 with m-CPBA/K2CO3. Of these oxaziridines the dichloro reagent 13b, available on a multigram scale, affords the highest enantioselectivities for the asymmetric oxidation of sulfides to sulfoxides (42-74%) and for the hydroxylation of enolates (often better than 95% ee). In general the molecular recognition is predicted and explained in terms of minimization of nonbonded steric interactions the transition states. For the asymmetric oxidation of sulfides to sulfoxides, secondary electronic factors related to the polarity of the sulfide and oxaziridine also play a role. Definitive evidence for chelation of the metal enolate with the C-X bond in 13 is not found. The molecular recognition is interpreted in terms of the higher reactivity of the reagents and an active-site structure which is sterically complementary with the enolate. For the asymmetric hydroxylation of the Z- and E-enolates of propiophenone (16a), the Z-enolate exhibits much higher stereoselectivity than the E-enolate: >95% vs 22% ee.