4,4-dimethyl-3-(2-naphthalenyl)-1-pentyn-3-ol

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4,4-dimethyl-3-(2-naphthalenyl)-1-pentyn-3-ol
• 英文别名: 4,4-dimethyl-3-(2-naphthyl)-1-pentyn-3-ol；3-(2'-naphthyl)-4,4-dimethyl-pent-1-yn-3-ol；4,4-Dimethyl-3-naphthalen-2-ylpent-1-yn-3-ol
• 化学式: C₁₇H₁₈O
• 分子量: 238.329
• InChiKey: AFAQTPUCJKPLOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  4,4-dimethyl-3-(2-naphthalenyl)-1-pentyn-3-ol 、 、 triethyloxonium hexaflourophosphate 以 二氯甲烷 为溶剂， 反应 2.0h， 以96%的产率得到
  参考文献：
  名称：

  Diastereoselective Attack on Chiral-at-Metal Ruthenium Allenylidene Complexes To Give Alkynyl Complexes

  摘要：

  New chiral ruthenium(II) allenylidene complexes were synthesized, and their reactivity with nucleophiles to give alkynyl complexes was investigated. The new allenylidene complex (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6){=C=C=C(t-Bu)(2-naphthyl)}]+PF6- was synthesized from the chloro precursor complex (R-Ru,R-ax)-[RuCl(Ind)(PPh3)(6)] and the racemic propargylic alcohol HC CC(OH)(t-Bu)(2-naphthyl) and obtained in 96% yield, where (Rax)-6 is a chiral phosphoramidite and Ind an anionic indenyl ligand. The precursor and the allenylidene complex are chiral-at-metal, and the chiral information is completely transferred from the chloro precursor to the product allenylidene complex, both of which show the same absolute configuration, as demonstrated by X-ray diffraction. Together with the known allenylidene complex (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6)(=C=C=CPh2)]+PF6-, the attack of n-BuLi, MeLi, LiC CPh, and lithium 1-phenylethenolate nucleophiles on the allenylidene chain of (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6){-C-C-C(t-Bu)(2-naphthyl)}]+PF6- was investigated. The nucleophiles (Nu) reacted selectively with the gamma carbon of the allenylidene complexes to give the alkynyl complexes (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6)(C CCPh(2)Nu)] and (R-Ru,R-Rax)-[Ru(Ind)(PPh3)(6){C CC(t-Bu)(2-naphthyl)Nu}] in 40% to 96% isolated yields. In the case of (R-Ru,R-Rax)-[Ru(Ind)(PPh3)(6){C CC*(t-Bu)(2-naphthyl)Nu}], the gamma carbon C* becomes stereogenic upon attack of the nucleophiles. As assessed by P-31{H-1} NMR, diastereodifferentiation took place, and the alkynyl complexes were isolated as diastereomeric mixtures with diastereomeric ratios between 60:40 and 84:16. The diastereodifferentiation originated only from the stereogenic metal center and the monodentate, chiral ligand. The study allows for investigation of stereoselective, nucleophilic attack of allenylidene complexes to give optically active, quaternary alkynes, which play a role in potential catalytic versions of nucleophilic substitution reactions of propargylic alcohols.

  DOI：

  10.1021/om500600y

文献信息

• Key factors in the synthesis of polycyclic iridaaromatics <i>via</i> the methoxyalkenylcarbene pathway
  作者：Maria Talavera、Krystal M. Cid-Seara、Ángeles Peña-Gallego、Sandra Bolaño

  DOI：10.1039/d1dt01361k

  日期：——

  Polycyclic iridaaromatic compounds are of great interest not only because of the contributions made in “aromatic chemistry”, but also because of the possibility of improving the results of the applications of the corresponding organic analogues in different fields. Therefore, understanding the requirements necessary to build on demand this type of compound with specific properties is of great importance

  多环环芳烃化合物引起人们极大的兴趣，不仅因为在“芳香化学”方面做出了贡献，还因为可以改善相应有机类似物在不同领域的应用结果。因此，了解按需构建具有特定属性的此类化合物的必要要求非常重要。在这项工作中，确定了通过甲氧基烯基卡宾成功合成环芳烃配合物的关键。实验和理论结果表明 (i) 在γ上带有两个芳香族取代基甲氧基烷基卡宾的碳促进 C-H 键活化；(ii) 选择性合成需要第二个取代基的大空间位阻，以及 (iii) C-H 键活化对空间位阻较小的系统的选择性。
• US4089908A
  申请人：——

  公开号：US4089908A

  公开（公告）日：1978-05-16
• Diastereoselective Attack on Chiral-at-Metal Ruthenium Allenylidene Complexes To Give Alkynyl Complexes
  作者：Matthew J. Queensen、Nigam P. Rath、Eike B. Bauer

  DOI：10.1021/om500600y

  日期：2014.10.13

  New chiral ruthenium(II) allenylidene complexes were synthesized, and their reactivity with nucleophiles to give alkynyl complexes was investigated. The new allenylidene complex (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6)=C=C=C(t-Bu)(2-naphthyl)}]+PF6- was synthesized from the chloro precursor complex (R-Ru,R-ax)-[RuCl(Ind)(PPh3)(6)] and the racemic propargylic alcohol HC CC(OH)(t-Bu)(2-naphthyl) and obtained in 96% yield, where (Rax)-6 is a chiral phosphoramidite and Ind an anionic indenyl ligand. The precursor and the allenylidene complex are chiral-at-metal, and the chiral information is completely transferred from the chloro precursor to the product allenylidene complex, both of which show the same absolute configuration, as demonstrated by X-ray diffraction. Together with the known allenylidene complex (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6)(=C=C=CPh2)]+PF6-, the attack of n-BuLi, MeLi, LiC CPh, and lithium 1-phenylethenolate nucleophiles on the allenylidene chain of (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6)-C-C-C(t-Bu)(2-naphthyl)}]+PF6- was investigated. The nucleophiles (Nu) reacted selectively with the gamma carbon of the allenylidene complexes to give the alkynyl complexes (R-Ru,R-ax)-[Ru(Ind)(PPh3)(6)(C CCPh(2)Nu)] and (R-Ru,R-Rax)-[Ru(Ind)(PPh3)(6)C CC(t-Bu)(2-naphthyl)Nu}] in 40% to 96% isolated yields. In the case of (R-Ru,R-Rax)-[Ru(Ind)(PPh3)(6)C CC*(t-Bu)(2-naphthyl)Nu}], the gamma carbon C* becomes stereogenic upon attack of the nucleophiles. As assessed by P-31H-1} NMR, diastereodifferentiation took place, and the alkynyl complexes were isolated as diastereomeric mixtures with diastereomeric ratios between 60:40 and 84:16. The diastereodifferentiation originated only from the stereogenic metal center and the monodentate, chiral ligand. The study allows for investigation of stereoselective, nucleophilic attack of allenylidene complexes to give optically active, quaternary alkynes, which play a role in potential catalytic versions of nucleophilic substitution reactions of propargylic alcohols.