3-methyl-2-(2-naphthalenyl)-2-butanol | 194865-21-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3-methyl-2-(2-naphthalenyl)-2-butanol
• 英文别名: 1,2-dimethyl-1-(2-naphthyl)-1-propanol；2-(2-Naphthyl)-3-methyl-butan-2-ol；3-methyl-2-naphthalen-2-ylbutan-2-ol
• CAS: 194865-21-9
• 化学式: C₁₅H₁₈O
• 分子量: 214.307
• InChiKey: IJCSTKOZADZZHK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  3-methyl-2-(2-naphthalenyl)-2-butanol 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 0.5h， 以82%的产率得到2-methyl-3-(2-naphthyl)-2-butene
  参考文献：
  名称：

  Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones

  摘要：

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.

  DOI：

  10.1021/jo970743b
• 作为产物：
  描述：

  异丙基溴化镁 、 2-萘乙酮 在 二乙二醇二甲醚 、 四丁基氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以80%的产率得到3-methyl-2-(2-naphthalenyl)-2-butanol
  参考文献：
  名称：

  格氏试剂与酮的无金属催化亲核加成反应

  摘要：

  在研究季铵盐和有机碱结合作用的基础上，开发了一种无金属添加的催化体系，用于在THF溶剂中将各种格氏试剂与各种酮类进行亲核加成反应，从而在乙醇中生产叔醇。好到极好的产量。通过使用氯化四丁基铵（NBu 4 Cl）作为催化剂和使用二甘醇二甲醚（DGDE）作为添加剂，该系统大大增强了添加效率，但又损失了烯醇化和还原作用。NBu 4Cl应有助于将Grignard试剂的Schlenk平衡移至二聚性Grignard试剂的一侧，以有利于通过有利的六元过渡态将Grignard试剂添加至酮上，以形成所需的叔醇，而DGDE应增加Cryignard试剂的亲核反应活性。格氏试剂经配比。该催化系统已被用于有效合成西酞普兰（一种有效的美国FDA批准的抗抑郁药），并且还设计了这种催化合成的可回收形式。

  DOI：

  10.1021/jo3004277

文献信息

• Highly Efficient Alkylation to Ketones and Aldimines with Grignard Reagents Catalyzed by Zinc(II) Chloride
  作者：Manabu Hatano、Shinji Suzuki、Kazuaki Ishihara

  DOI：10.1021/ja0628405

  日期：2006.8.1

  efficient alkylation to ketones and aldimines with Grignard reagents in the presence of catalytic trialkylzinc(II) ate complexes derived from ZnCl2 (10 mol %) in situ was developed. This simple Zn(II)-catalyzed alkylation could minimize the well-known but serious problems with the use of only Grignard reagents, which leads to reduction and aldol side products, and the yield of desired alkylation products

  在由 ZnCl2 (10 mol%) 衍生的催化三烷基锌 (II) 酸酯配合物的存在下，使用格氏试剂高效地烷基化为酮和醛亚胺。这种简单的 Zn(II) 催化烷基化可以最大限度地减少仅使用格氏试剂而导致还原和羟醛副产物的众所周知但严重的问题，并且可以提高所需烷基化产物的产率。
• ——
  作者：Yu. V. Shklyaev

  DOI：10.1023/a:1023712223277

  日期：——
• Added-Metal-Free Catalytic Nucleophilic Addition of Grignard Reagents to Ketones
  作者：Hua Zong、Huayin Huang、Junfeng Liu、Guangling Bian、Ling Song

  DOI：10.1021/jo3004277

  日期：2012.5.18

  reagents to the side of dimeric Grignard reagents to favor the additions of Grignard reagents to ketones via a favored six-membered transition state to form the desired tertiary alcohols, and DGDE should increase the nucleophilic reactivities of Grignard reagents by coordination. This catalytic system has been applied in the efficient synthesis of Citalopram, an effective U.S. FDA-approved antidepressant

  在研究季铵盐和有机碱结合作用的基础上，开发了一种无金属添加的催化体系，用于在THF溶剂中将各种格氏试剂与各种酮类进行亲核加成反应，从而在乙醇中生产叔醇。好到极好的产量。通过使用氯化四丁基铵（NBu 4 Cl）作为催化剂和使用二甘醇二甲醚（DGDE）作为添加剂，该系统大大增强了添加效率，但又损失了烯醇化和还原作用。NBu 4Cl应有助于将Grignard试剂的Schlenk平衡移至二聚性Grignard试剂的一侧，以有利于通过有利的六元过渡态将Grignard试剂添加至酮上，以形成所需的叔醇，而DGDE应增加Cryignard试剂的亲核反应活性。格氏试剂经配比。该催化系统已被用于有效合成西酞普兰（一种有效的美国FDA批准的抗抑郁药），并且还设计了这种催化合成的可回收形式。
• Palladium-Catalyzed Isomerization of Aryl-Substituted Epoxides:  A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones
  作者：Sanjitha Kulasegaram、Robert J. Kulawiec

  DOI：10.1021/jo970743b

  日期：1997.9.1

  Aryl-substituted epoxides bearing multiple methyl substituents on the epoxide ring isomerize in the presence of 5 mol % Pd(OAc)(2)PR3 (R = n-Bu, Ph) to form the corresponding benzylic aldehyde or ketone, with complete regioselectivity for the carbonyl compound formed via cleavage of the benzylic C-O bond. No allylic alcohols or products arising from alkyl migration are observed. Rapid reaction rates and nearly quantitative yields are obtained, even with highly sterically hindered epoxides, using tri-n-butylphosphine as ligand and tert-butyl alcohol as solvent. 2-Aryl-substituted epoxides with two methyl substituents on C3 are completely unreactive, consistent with an oxidative addition/beta-hydride elimination mechanism. Catalyst variation studies show that both Pd(OAc)(2) and PR3 are essential for optimal activity and that palladium catalysts formed in this manner are superior to other Pd(O) catalysts (e.g., Pd(PPh3)(4)). The reactivity of catalytic Pd(OAc)(2)/PR3 toward multiply-substituted epoxides is compared to traditional Lewis acid catalysts; the former is found to be much more selective for isomerization without skeletal rearrangement. A mechanistic rationale involving turnover-limiting S(N)2-like attack of Pd(O) at the benzylic carbon is proposed.