5-benzoyl-4-hydroxy[2.2]paracyclophane | 595561-04-9

• 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: 5-benzoyl-4-hydroxy[2.2]paracyclophane
• 英文别名: (6-Hydroxy-5-tricyclo[8.2.2.24,7]hexadeca-1(13),4,6,10(14),11,15-hexaenyl)-phenylmethanone
• CAS: 595561-04-9
• 化学式: C₂₃H₂₀O₂
• 分子量: 328.411
• InChiKey: GMCLHGYSJVHFFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  5-benzoyl-4-hydroxy[2.2]paracyclophane 在 CuCl(OH)-TMEDA 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 5,5'-dibenzoyl-7,7'-bis[2.2]paracyclophan-4,4'(7H,7'H)-dione
  参考文献：
  名称：

  [2.2] 对环芳烃衍生酚的溶剂依赖性区域和立体选择性氧化

  摘要：

  用 Cu(OH)Cl·TMEDA 氧化 4-羟基 [2.2] 对环烷及其衍生物后形成的产物的结构取决于所用的溶剂。在 MeOH 中，氧化伴随着溶剂的亲核攻击，主要或仅提供具有 (Rp*,Rp*) 相关构型的邻环己二烯酮（邻羟基喹啉甲基醚）。在 CH2Cl2 中进行的氧化导致对环己二烯酮二聚体{各种取代的 7,7'-双[2.2]对环芳-4,4'(7H,7'H)-二酮}与 (Sp*, Rc*,Rc*,Sp*) 相对和 (Rp,Sc,Rc,Sp) 绝对构型（每种情况下六种可能的非对映体中的两种），而对映体纯苯酚的氧化产生各自的单一产物。

  DOI：

  10.1002/ejoc.201501565
• 作为产物：
  描述：

  对二甲苯二聚体 在 正丁基锂 、 溴 、 四氯化钛 、 铁粉 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 5-benzoyl-4-hydroxy[2.2]paracyclophane
  参考文献：
  名称：

  Preparation of planar chiral amino phenols based on the [2.2]paracyclophane backbone

  摘要：

  The synthesis of various planar and central chiral secondary and tertiary amino phenols based on the [2.2]paracyclophane backbone is described, Planar chiral tertiary amino phenols are prepared by reductive amination of 5-formyl-4-hydroxy[2,2]paracyclophane (FHPC) with secondary amines, The reduction of imine and ketimine precursors, as well as the 1,2-addition to these compounds is also described. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00497-9

文献信息

• Structurally Diverse Second-Generation [2.2]Paracyclophane Ketimines with Planar and Central Chirality: Syntheses, Structural Determination, and Evaluation for Asymmetric Catalysis
  作者：Frank Lauterwasser、Martin Nieger、Heidi Mansikkamäki、Kalle Nättinen、Stefan Bräse

  DOI：10.1002/chem.200500146

  日期：2005.7.18

  A set of 20 novel [2.2]paracyclophane ketimines with planar and central chirality has been synthesized from enantiomerically pure and racemic 5-acyl-4-hydroxy[2.2]paracyclophane and alpha-branched chiral amines. Their X-ray structures were determined to elucidate the three-dimensional structures and the absolute configuration. The ketimines were used as catalysts in the asymmetric 1,2-addition reactions

  由对映体纯的和外消旋的5-酰基-4-羟基[2.2]对环环糊精和α-支化手性胺合成了一组20种具有平面和中心手性的新型[2.2]对环环酮酮。确定其X射线结构以阐明三维结构和绝对构型。酮亚胺在二乙基锌与取代的苯甲醛的不对称1,2-加成反应中用作催化剂，以提供高达95％ee的手性醇。
• Synthesis of novel planar-chiral [2.2]paracyclophane derivatives as potential ligands for asymmetric catalysis
  作者：Michael Kreis、Martin Nieger、Stefan Bräse

  DOI：10.1016/j.jorganchem.2005.10.031

  日期：2006.5

  The synthesis of a variety of new 4,5-disubstituted [2.2]paracyclophane derivatives has been achieved employing different cross-coupling reactions. By this methodology, a heteroatom-variation of successful catalyst ligands was achieved, giving rise to a modular ligand system. The X-ray structure of 4-hydroxy-5-(1′-hydroxy-1′-phenylethyl)-[2.2]paracyclophane was determined to elucidate the configuration

  已经使用不同的交叉偶联反应实现了多种新的4，5-二取代的[2.2]对环环烷衍生物的合成。通过这种方法，成功的催化剂配体实现了杂原子变异，从而产生了模块化的配体体系。确定4-羟基-5-（1'-羟基-1'-苯乙基）-[2.2]对环烷的X射线结构以阐明其构型。另外，实现了平面和中心手性的4-（[2.2]对环苯甲酰基）乙胺的非对映选择性合成，因此得到了平面和中心手性的苯基乙胺类似物。
• Novel ligands based on bromosubstituted hydroxycarbonyl [2.2]paracyclophane derivatives: synthesis and application in asymmetric catalysis
  作者：Natalia V. Vorontsova、Galina S. Bystrova、Dmitrii Yu. Antonov、Anna V. Vologzhanina、Ivan A. Godovikov、Michail M. Il’in

  DOI：10.1016/j.tetasy.2010.03.038

  日期：2010.4

  planar-chiral hydroxycarbonyl [2.2]paracyclophane derivatives, 4-acetyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-АНРС, 63%) and 4-benzoyl-13-bromo-5-hydroxy[2.2]paracyclophane (Br-BHPC, 53%), were synthesized and reacted with the enantiomers of α-phenylethylamine to form corresponding Schiff bases, 12-bromo-4-hydroxy-5[1-(1-phenyl-ethylimino)-ethyl]-[2.2]paracyclophane and 12-bromo-4-hydroxy-5[1-(1

  新的平面手性羟羰基[2.2]对环环烷衍生物，4-乙酰基-13-溴-5-羟基[2.2]对环环烷（Br-АНРС，63％）和4-苯甲酰基-13-溴-5-羟基[2.2]对环烷（Br-BHPC，53％）被合成并与α-苯基乙胺的对映异构体反应以形成相应的席夫碱，即12-溴-4-羟基-5 [1-（1-苯基-乙基亚氨基）-乙基]-[ 2.2]对环环烷和12-溴-4-羟基-5 [1-（1-苯基-乙基亚氨基）-（苯基）亚甲基-[2.2]对环环烷。解析了亚胺的非对映异构体，并通过X射线衍射确定了其绝对构型，进而确定了Br-АНРС对映体的相应构型。
• Planar-chiral salen and hemisalen [2.2]paracyclophane ligands for asymmetric diethylzinc addition to aldehydes
  作者：Tatyana I. Danilova、Valeria I. Rozenberg、Zoya A. Starikova、Stefan Bräse

  DOI：10.1016/j.tetasy.2003.11.031

  日期：2004.1

  multistereogenic symmetric and asymmetric salens based on a [2.2]paracyclophane skeleton have been tested as catalysts for the enantioselective addition of diethylzinc to aldehydes affording the corresponding alcohols in up to 94% enantiomeric excess. Chiral [2.2]paracyclophane hemisalens are applied for the first time as chiral ligands in the Et2Zn addition to benzaldehyde.

  已经测试了基于[2.2]对环环烷骨架的14种多体对称和不对称Salen，作为将二乙基锌对映体选择性加成到醛类中的催化剂，相应的醇的对映体过量高达94％。首次将手性[2.2]对环环烷半缩醛作为苯甲醛中Et 2 Zn中的手性配体使用。
• Kinetic Resolution of [2.2]Paracyclophane-Derived Cyclic <i>N</i>-Sulfonylimines via Palladium-Catalyzed Addition of Arylboronic Acids
  作者：Yang Zhao、Xiao-Qing Wang、Yan-Jiang Yu、Yong-Gui Zhou

  DOI：10.1021/acs.joc.0c02509

  日期：2021.1.1

  A facile method for kinetic resolution of [2.2]paracyclophane-derived cyclic N-sulfonylimines based on palladium-catalyzed addition of arylboronic acids was developed, giving two kinds of planar chiral [2.2]paracyclophane derivatives in excellent diastereoselectivities and up to 99% of enantioselectivities with high selectivity factors (s up to 128).

  开发了一种基于钯催化的芳基硼酸加成反应的[2.2]对环环糊精衍生的环状N-磺酰亚胺类化合物的动力学拆分的简便方法，得到了两种平面手性[2.2]对环环糊精衍生物，具有优异的非对映选择性和高达99％的对映选择性以高选择性的因素（š高达128）。