3,3,5-trimethyl-2H-furan | 1401111-16-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: 3,3,5-trimethyl-2H-furan
• CAS: 1401111-16-7
• 化学式: C₇H₁₂O
• 分子量: 112.172
• InChiKey: PFOCOISDHQQLFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  (-)-薄荷酮 、 3,3,5-trimethyl-2H-furan 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 以91%的产率得到(1R,2S,5R)-1-((4,4-dimethyl-4,5-dihydrooxazol-2-yl)methyl)-2-isopropyl-5-methylcyclohexanol
  参考文献：
  名称：

  Stereoselective Addition of Diethylzinc to Aldehydes Using Chiral β-Hydroxy-2-oxazolines as Catalysts

  摘要：

  Chiral beta-hydroxy-2-oxazolines were synthesized and evaluated as catalysts for the addition of diethylzinc to aldehydes. All oxazolines proved effective in obtaining the addition products. The best enantiomeric excesses (69-78%) were obtained using the chiral beta-hydroxy oxazoline derived from (-)-menthone and the amino alcohol 2-amino-2-methylpropan-1-ol.

  DOI：

  10.5935/0103-5053.20140233
• 作为产物：
  描述：

  2,2-Dimethyl-3,4-pentadien-1-ol 反应 0.5h， 生成 3,3,5-trimethyl-2H-furan
  参考文献：
  名称：

  Alkaline Earth Catalysis of Alkynyl Alcohol Hydroalkoxylation/Cyclization

  摘要：

  Heavier alkaline earth bis(trimethylsilyl)amides [Ae{N(SiMe3)(2)}(2)](2) (Ae = Ca, Sr, Ba) are shown to act as effective precatalysts for the regioselective intramolecular hydroalkoxylation/cyclization of a wide range of alkynyl and allenyl alcohols. In the majority of cases, cyclization of alkynyl alcohols produces mixtures of the possible endo- and exocyclic enol ether products, rationalized as a consequence of alkynylalkoxide isomerization to the corresponding allene derivatives. Cyclization rates for terminal alkynyl alcohols were found to be significantly higher than for substrates bearing internal alkynyl substituents, while the efficacy of cyclization was in general found to be determined by a combination of stereoelectronic influences and the thermochemical viability of the specific alkaline earth metal catalysis, which we suggest is determined by the individual M-O bond strengths. Kinetic studies have provided a rate law pertaining to a pronounced catalyst inhibition with increasing [substrate], indicating that turnover-limiting insertion of C-C unsaturation into the M-O bond requires the dissociation of substrate molecules away from the Lewis acidic alkaline earth center.

  DOI：

  10.1021/om3008663

文献信息

• Discovery of a Photoinduced Dark Catalytic Cycle Using <i>in Situ</i> LED-NMR Spectroscopy
  作者：Dan Lehnherr、Yining Ji、Andrew J. Neel、Ryan D. Cohen、Andrew P. J. Brunskill、Junyu Yang、Mikhail Reibarkh

  DOI：10.1021/jacs.8b08596

  日期：2018.10.24

  We report the use of LED-NMR spectroscopy to study the reaction mechanism of a newly discovered photoinduced iron-catalyzed cycloisomerization of alkynols to cyclic enol ethers. By understanding on/off ligand binding to the catalyst, we were able to appropriately design reaction conditions to balance catalyst activity and stability. LED-NMR was demonstrated to be a powerful tool in elucidating reaction mechanisms of photochemical reactions. Temporal NMR spectroscopic data under visible light illumination (1) revealed the pre-catalyst activation mechanism, (2) proved that photon flux provides a unique external control of the equilibrium distribution between the pre-catalyst and active catalyst, and ultimately the rate of reaction, (3) provided information about the reaction driving forces and the turnover-limiting step, and (4) enabled both real-time structural and kinetic insights into elusive species (e.g., dissolved gases).
• Alkaline Earth Catalysis of Alkynyl Alcohol Hydroalkoxylation/Cyclization
  作者：Christine Brinkmann、Anthony G. M. Barrett、Michael S. Hill、Panayiotis A. Procopiou、Stephanie Reid

  DOI：10.1021/om3008663

  日期：2012.10.22

  Heavier alkaline earth bis(trimethylsilyl)amides [AeN(SiMe3)(2)}(2)](2) (Ae = Ca, Sr, Ba) are shown to act as effective precatalysts for the regioselective intramolecular hydroalkoxylation/cyclization of a wide range of alkynyl and allenyl alcohols. In the majority of cases, cyclization of alkynyl alcohols produces mixtures of the possible endo- and exocyclic enol ether products, rationalized as a consequence of alkynylalkoxide isomerization to the corresponding allene derivatives. Cyclization rates for terminal alkynyl alcohols were found to be significantly higher than for substrates bearing internal alkynyl substituents, while the efficacy of cyclization was in general found to be determined by a combination of stereoelectronic influences and the thermochemical viability of the specific alkaline earth metal catalysis, which we suggest is determined by the individual M-O bond strengths. Kinetic studies have provided a rate law pertaining to a pronounced catalyst inhibition with increasing [substrate], indicating that turnover-limiting insertion of C-C unsaturation into the M-O bond requires the dissociation of substrate molecules away from the Lewis acidic alkaline earth center.
• Stereoselective Addition of Diethylzinc to Aldehydes Using Chiral β-Hydroxy-2-oxazolines as Catalysts
  作者：Francisco A. Marques、Celso L. Wosch、Gustavo Frensch、Ricardo Labes、Beatriz H. L. N. S. Maia、Kahlil S. Salomé、Andersson Barison、Palimécio G. Guerrero Jr.

  DOI：10.5935/0103-5053.20140233

  日期：——

  Chiral beta-hydroxy-2-oxazolines were synthesized and evaluated as catalysts for the addition of diethylzinc to aldehydes. All oxazolines proved effective in obtaining the addition products. The best enantiomeric excesses (69-78%) were obtained using the chiral beta-hydroxy oxazoline derived from (-)-menthone and the amino alcohol 2-amino-2-methylpropan-1-ol.