3-adamantyl-5-tert-butyl-2-hydroxybenzaldehyde | 801288-07-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-adamantyl-5-tert-butyl-2-hydroxybenzaldehyde
• 英文别名: 3-(1-Adamantyl)-5-tert-butyl-2-hydroxybenzaldehyde
• CAS: 801288-07-3
• 化学式: C₂₁H₂₈O₂
• 分子量: 312.452
• InChiKey: HSRIYVRXGRACPE-UHFFFAOYSA-N

物化性质

• 熔点：
  128-130 °C
• 沸点：
  397.5±42.0 °C(Predicted)
• 密度：
  1.135±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-adamantyl-5-tert-butyl-2-hydroxybenzaldehyde 、 (1R,2R)-(-)-N-(对甲基苯磺酰基)-1,2-二苯基乙二胺 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 以2.68 g的产率得到
  参考文献：
  名称：

  稀土金属酰胺 RE[N(SiMe3)2]3 与苯氧基官能化 TsDPEN 配体催化丙二腈与不饱和酮的对映选择性迈克尔加成

  摘要：

  使用稀土金属酰胺 RE[N(SiMe 3 ) 2 ] 3 (RE = Y, Eu, Sm, Nd, La) 和手性苯氧基，很好地建立了 α,β-不饱和酮与丙二腈的催化对映选择性迈克尔加成反应。功能化的 TsDPEN 配体。酰胺镧 La[N(SiMe 3 ) 2 ] 3与手性 TsDPEN 配体 H 3 L 1 [H 3 L 1 = N -((1 R ,2 R )-2-((3,5-di-)叔丁基-2-羟基苄基)氨基)-1,2-二苯基乙基)-4-甲基苯磺酰胺]以1:1.5的摩尔比被证明是THF的最佳配合物，它以优异的产率提供了所需的β-羰基二腈-15 °C 12 小时后具有良好至高的对映选择性。

  DOI：

  10.1021/acs.joc.3c01435
• 作为产物：
  描述：

  4-叔丁基苯酚 在 硫酸 、 三乙胺 、 magnesium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.5h， 生成 3-adamantyl-5-tert-butyl-2-hydroxybenzaldehyde
  参考文献：
  名称：

  Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Amides [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ with Phenoxy-Functionalized Chiral Prolinols

  摘要：

  A simple and efficient catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been successfully developed, which was catalyzed by rare-earth metal amides [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb (1), La (2), Sm (3), Y (4), Lu (5)) in the presence of phenoxy-functionalized chiral prolinols at room temperature using tert-butylhydroperoxide (TBHP) as the oxidant. The combination of an Yb-based amide 1 and a chiral proligand (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol) performed very well, and both the yields and the enantiomeric excess of the chiral epoxides reached up to 99% and 99% ee.

  DOI：

  10.1021/acs.orglett.5b00833

文献信息

• Mechanism-Inspired Design of Bifunctional Catalysts for the Alternating Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides
  作者：Brooks A. Abel、Claire A. L. Lidston、Geoffrey W. Coates

  DOI：10.1021/jacs.9b05570

  日期：2019.8.14

  bifunctional complex in which the salen catalyst and an aminocyclopropenium cocatalyst are covalently tethered. A modular ligand design circumvents the extended linear syntheses typical of bifunctional catalysts, enabling systematic variation to understand and enhance catalytic activity. The optimized bifunctional aluminum salen catalyst maintains excellent activity for the ring-opening copolymerization of epoxides

  催化方面的进步使环氧化物和环状酸酐的开环共聚能够提供具有可控分子量和分散性的结构和功能多样的聚酯。然而，最常见的系统采用二元催化剂/助催化剂对，其在低负载下聚合速率慢。受对低浓度二元金属 salen/亲核助催化剂系统功能的新机制洞察的启发，我们报告了一种双功能复合物，其中 salen 催化剂和氨基环丙烯助催化剂共价连接。模块化配体设计绕过了双功能催化剂典型的扩展线性合成，使系统变异能够理解和增强催化活性。
• Enantioselective Hydroboration of Ketones Catalyzed by Rare-Earth-Metal Complexes Supported with Phenoxy-Functionalized TsDPEN Ligands
  作者：Qishun Yu、Chengrong Lu、Bei Zhao

  DOI：10.1021/acs.organomet.1c00272

  日期：2021.8.9

  Six novel chiral rare-earth-metal complexes bearing the phenoxy-functionalized TsDPEN ligand H3L1 (H3L1 = N-((1R,2R)-2-((3,5-di-tert-butyl-2-hydroxybenzyl)amino)-1,2-diphenylethyl)-4-methylbenzenesulfonamide) were synthesized successfully and well characterized. The solid-state structures of four tetranuclear rare-earth-metal complexes [RE2L13]2 (RE = Nd (1), Sm (2), Eu (3), Gd (4)) and the dual-core

  六新型手性稀土类金属络合物轴承苯氧基官能化TsDPEN配位体H 3大号1（H 3大号1 = ñ - （（1 - [R，2 - [R）-2 - （（3,5-二-叔丁基-2-羟基苄基）氨基）-1,2-二苯基乙基）-4-甲基苯磺酰胺）已成功合成并得到很好的表征。四种四核稀土金属配合物[RE 2 L 1 3 ] 2 (RE = Nd ( 1 ), Sm ( 2 ), Eu ( 3 ), Gd ( 4 ))和双核的固态结构钇配合物 Y 2L 1 3 ( 5 ) 分别由X-射线衍射测定。镧配合物6的结构由THF- d 8中的1 H DOSY光谱以及DFT计算推测。配合物1 - 5被用于催化使用频哪醇（HBpin）作为还原剂酮和α，β不饱和酮的对映选择性硼氢化，和复杂1相比于其他人给出了更好的结果。以极好的收率和适中的ee值获得了相应的仲醇。使用钕酰胺 Nd[N(SiMe3 ) 2 ] 3与苯氧基官能化的TsDPEN配体H
• Co-Metal-Free Enantioselective Conjugate Addition Reactions of Zinc Reagents
  作者：Sefer Ay、Martin Nieger、Stefan Bräse

  DOI：10.1002/chem.200801676

  日期：——

  Asymmetric conjugate addition of diethylzinc to cinnamaldehyde in a co-metal-free fashion by using N,O-ligands with planar and central chirality is described. Different modulations of the ligand structure, including several combinations of the chiral units, indicate that a [2.2]paracyclophane backbone is essential for the activity and the enantioselectivity of the generated active catalyst. By using

  描述了通过使用具有平面和中心手性的N，O-配体，以无共金属的方式将二乙基锌不对称地共轭添加到肉桂醛中。配体结构的不同调节，包括手性单元的几种组合，表明[2.2]对环烷骨架对所产生的活性催化剂的活性和对映选择性是必不可少的。通过使用优化的配体，分离出的产率为90％，ee高达99％。
• Large ultra-high molecular weight polyethylene spherical particles produced by AlR3 activated half-sandwich chromium(iii) catalysts
  作者：Mingtai Sun、Tieqi Xu、Wei Gao、Yang Liu、Qiaolin Wu、Ying Mu、Ling Ye

  DOI：10.1039/c1dt10659g

  日期：——

  A series of half-sandwich pentamethylcyclopentadienyl chromium(III) complexes bearing a salicylaldiminato ligand, Cp*[2-R1-4-R2-6-(CHNR3)C6H2O]CrCl [R1 = iPr (1, 4), tBu (2, 3, 5), Ad (6); R2 = H (1, 2, 3), tBu (4, 5, 6); R3 = iPr (1, 2, 5, 6), tBu (3, 4)], were synthesized. All complexes were characterized by elemental analyses and the structures of complexes 1–4 and 6 were determined by X-ray diffraction analysis. These complexes adopt a pseudo-octahedral coordination environment with a three-legged piano stool geometry. Upon activation with a small amount of AlR3, complexes 1–6 all catalyze the polymerization of ethylene in a quasi living fashion with good to high catalytic activity under mild conditions and produce ultra-high molecular weight polyethylene as spherical particles with a diameter of 1–6 mm. The catalytic activity of these complexes and the molecular weight of the produced polyethylene can be tuned in a broad range by changing the R1, R2, and R3groups as well as the AlR3 cocatalyst. It was found that complex 6 with R1 = Ad, R2 = tBu, and R3 = iPr shows the highest catalytic activity and produces polyethylene with the highest molecular weight.

  合成了一系列半夹心的五甲基环戊二烯铬(III)配合物，该配合物具有水杨醛亚胺配体，Cp*[2-R1-4-R2-6-(CHNR3)C6H2O]CrCl [R1 = iPr (1, 4), tBu (2, 3, 5), Ad (6); R2 = H (1, 2, 3), tBu (4, 5, 6); R3 = iPr (1, 2, 5, 6), tBu (3, 4)]。所有配合物均通过元素分析进行表征，配合物1–4和6的结构通过X射线衍射分析确定。这些配合物采用伪八面体配位环境，具有三脚钢琴凳几何结构。在激活AlR3少量的情况下，配合物1–6均能以近生的方式催化乙烯聚合，在温和条件下表现出良好至高的催化活性，产生直径为1–6毫米的超高分子量聚乙烯球形颗粒。通过改变R1、R2、R3基团以及AlR3助催化剂，可以在宽范围内调节这些配合物的催化活性和所生成聚乙烯的分子量。发现配合物6（R1 = Ad, R2 = tBu, R3 = iPr）具有最高的催化活性，并生成具有最高分子量的聚乙烯。
• Asymmetric hydroamination catalyzed by a new chiral zirconium system: reaction scope and mechanism
  作者：Xiaoguang Zhou、Bing Wei、Xiu-Li Sun、Yong Tang、Zuowei Xie

  DOI：10.1039/c4cc10032h

  日期：——

  A new class of pincer-like chiral [O⁻NO⁻]ZrR₂ systems has been developed for efficient asymmetric hydroamination of primary aminoalkenes with up to 94% ee and ≥95% conversion.

  一种新的类似钳状的手性[O⁻NO⁻]ZrR₂系统已经开发出来，用于高效的一次氨烯烃不对称氢胺化反应，产率可达94%的对映选择性和≥95%的转化率。