(R)-3,3'-bis(chloroformyl)-2,2'-dimethoxy-1,1'-binaphthyl

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-3,3'-bis(chloroformyl)-2,2'-dimethoxy-1,1'-binaphthyl
• 英文别名: (R)-2,2'-dimethoxy-3,3'-dichlorocarbonyl-1,1'-binaphthyl；4-(3-carbonochloridoyl-2-methoxynaphthalen-1-yl)-3-methoxynaphthalene-2-carbonyl chloride
• 化学式: C₂₄H₁₆Cl₂O₄
• 分子量: 439.295
• InChiKey: QWULKMPVGAQYAC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-3,3'-bis(chloroformyl)-2,2'-dimethoxy-1,1'-binaphthyl 在 sodium azide 作用下， 以 水 、 丙酮 为溶剂， 反应 0.25h， 生成 4-(3-Carbonazidoyl-2-methoxynaphthalen-1-yl)-3-methoxynaphthalene-2-carbonyl azide
  参考文献：
  名称：

  BINOL-Based FoldamersAccess to Oligomers with Diverse Structural Architectures

  摘要：

  In this article, we report on the synthesis and conformation of a new family of aromatic oligoamide foldamers based on binaphthol (BINOL) monomers. A series of oligomers with differing chirality of the individual BINOL building blocks and mixed sequences of alternate BINOL and pyridyl building blocks has been synthesized and structurally characterized. NMR and quantum chemical calculations on the basis of ab initio MO theory were performed to obtain insight into the conformational features of these oligomers. It is shown that the combination of these inherently chiral aromatic building blocks provides a novel access to a wide variety of conformationally ordered synthetic oligomers with diverse and dazzling structural architectures distinct from those classically observed.

  DOI：

  10.1021/jo070396y
• 作为产物：
  描述：

  2-羟基-3-萘甲酸 在 氢氧化钾 、 草酰氯 、 硫酸 、 potassium carbonate 、 N,N-二甲基甲酰胺 作用下， 以 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 84.0h， 生成 (R)-3,3'-bis(chloroformyl)-2,2'-dimethoxy-1,1'-binaphthyl
  参考文献：
  名称：

  BINOL-Based FoldamersAccess to Oligomers with Diverse Structural Architectures

  摘要：

  In this article, we report on the synthesis and conformation of a new family of aromatic oligoamide foldamers based on binaphthol (BINOL) monomers. A series of oligomers with differing chirality of the individual BINOL building blocks and mixed sequences of alternate BINOL and pyridyl building blocks has been synthesized and structurally characterized. NMR and quantum chemical calculations on the basis of ab initio MO theory were performed to obtain insight into the conformational features of these oligomers. It is shown that the combination of these inherently chiral aromatic building blocks provides a novel access to a wide variety of conformationally ordered synthetic oligomers with diverse and dazzling structural architectures distinct from those classically observed.

  DOI：

  10.1021/jo070396y

文献信息

• Shape selectivity in the synthesis of chiral macrocyclic amides
  作者：Stefano Colombo、Carmine Coluccini、Marco Caricato、Claudia Gargiulli、Giuseppe Gattuso、Dario Pasini

  DOI：10.1016/j.tet.2010.03.102

  日期：2010.6

  convergent methodology. The source of chirality, an axially-chiral Binol scaffold, incorporates methoxy functionalities in the 2,2′ positions, and carboxylic functionalities in the external 3,3′ positions. The latter can be efficiently elaborated through aromatic amidation to introduce aromatic spacers of differing shapes. The peculiar arrangement of functionalities on the Binol skeleton functions as an element

  形状持久的旋光性芳基酰胺大环化合物已通过逐步收敛的方法进行了设计和研究。手性的来源是轴向手性的Binol支架，在2,2'位具有甲氧基官能度，在外部3,3'位具有羧基官能度。可以通过芳族酰胺化有效地修饰后者，以引入不同形状的芳族间隔基。在二元醇骨架上特殊的功能排列是通过形成稳定的分子内氢键而使共价结构刚性化的元素。当通过使用柔性的3,3'-二氨基联苯作为间隔基来平衡该元素时，大环化步骤的收率增加到高于50％的值。
• Versatile and Practical Macrocyclic Reagent with Multiple Hydrogen-Bonding Sites for Chiral Discrimination in NMR
  作者：Tadashi Ema、Daisuke Tanida、Takashi Sakai

  DOI：10.1021/ja073476s

  日期：2007.8.1

  the best chiral solvating agent (shift reagent), which is effective for a wide range of chiral compounds having a carboxylic acid, oxazolidinone, carbonate, lactone, alcohol, sulfoxide, sulfoximine, sulfinamide, isocyanate, or epoxide functionality. The addition of only 5 mol % (69 microg, 0.15 mM) of 1 splits the enantiomeric signals of sulfoxide 13. The excellent performance of 1 as a chiral solvating

  设计并合成了双功能大环 1-4 和二酰胺 5。核磁共振研究表明，其中，受体1作为最好的手性溶剂化剂（移位试剂），对多种手性化合物有效，包括羧酸、恶唑烷酮、碳酸酯、内酯、醇、亚砜、亚砜亚胺、亚磺酰胺、异氰酸酯或环氧化物官能团。仅添加 5 mol % (69 microg, 0.15 mM) 的 1 即可分裂亚砜 13 的对映体信号。 1 作为手性溶剂化剂的优异性能，如通用性、信号锐度、高分裂能力、高灵敏度、宽报告了检测窗口和合成可访问性。核磁共振研究表明，1 的主要结合位点是下段的两个酰胺 NH 基团，另外的结合位点是吡啶基氮。发现 1 中构建的两个 2,6-二酰基氨基吡啶部分的 V 形排列对于结合多种化合物比 4 中构建的两个结合基序的平行排列更有效。 1 中的 NO2 基团不仅增强了结合能力，而且增强了对映选择性。出乎意料的是，1 和 3 之间的比较使我们能够发现联萘部分的相对取向的重要
• Properties of a Binaphthyl-bridged Porphyrin–Iron Complex Bearing Hydroxy Groups inside its Cavity
  作者：Alain Kossanyi、Fumito Tani、Nobu Nakamura、Yoshinori Naruta

  DOI：10.1002/1521-3765(20010702)7:13<2862::aid-chem2862>3.0.co;2-k

  日期：2001.7.2

  basic ligands, dioxygen and carbon monoxide has been studied. When a bulky axial ligand such as 1-methyladamantyl-2-methylimidazole is used, only the pentacoordinated complex is obtained, and, as expected, dioxygen binds as the sixth ligand only in the cavity of the compound. Under unusually low dioxygen partial pressures and in rigorously anhydrous toluene, the pentacoordinated iron complex is completely

  带有末端氧原子的氢键形成被认为是细胞色素P450激活双氧分子的基础。为了验证该氢键的作用，我们进行了模型配合物的合成：在适当位置（“单冠”或“ SC”）带有羟基的双萘基桥连卟啉。已经研究了合成化合物的铁络合物对碱性配体，双氧和一氧化碳的反应性。当使用大体积的轴向配体如1-甲基金刚烷基-2-甲基咪唑时，仅获得五配位配合物，并且如所预期的，双氧仅作为第六配体结合在化合物的空腔中。在异常低的双氧分压和严格的无水甲苯中，五配位的铁络合物被完全转化为一个新物种，该新物种在420和559 nm的可见光区域吸收，并且我们已将其鉴定为含氧化合物。出乎意料的是，该反应似乎是不可逆地发生的，这是基于以下事实：在将氮气鼓泡通过溶液数小时后，最初的络合物没有被回收。另一方面，用一氧化碳饱和溶液可将络合物缓慢但完全地转变为Fe（II）-CO络合物，该络合物在0摄氏度的双氧饱和甲苯溶液中稳定。但是，通过升高温度，自发
• Synthesis of 2,2'-Bipyridines with Axially Chiral 1,1'-Binaphthalene Units
  作者：Jana Hodačová、Ivan Stibor

  DOI：10.1135/cccc20000083

  日期：——

  Synthesis of a series of novel 2,2'-bipyridine-based ligands bearing the axially chiral 2,2'-dialkoxy-1,1'-binaphthalene units is presented. The oxydimethylene, amidomethylene and amido spacers have been utilised to link the 3 or 3,3' positions of the binaphthalene skeleton with the 6 or 6,6' positions of the 2,2'-bipyridine moieties. The ligands have been synthesised in both racemic and enantiomerically pureRforms.

  本文介绍了一系列新型2,2'-联吡啶配基的合成，这些配基带有轴手性的2,2'-二烷氧基-1,1'-联萘基团。氧二甲基、酰胺甲基和酰胺间隔被用来连接联萘骨架的3或3,3'位置和2,2'-联吡啶基团的6或6,6'位置。这些配基既可以合成为外消旋体，也可以合成为对映纯的R形式。
• Chiral "basket handle" binaphthyl porphyrins: synthesis, catalytic epoxidation and NMR conformational studies
  作者：Eric Rose、Emma Gallo、Nicolas Raoul、Léa Bouché、Ariane Pille、Alessandro Caselli、Olivier Lequin

  DOI：10.1142/s1088424610002483

  日期：2010.7

  Three "basket handle" porphyrins have been prepared by condensation of tetrakis-(α,β,α,β-2-aminophenyl)porphyrin atropoisomer with 1,1′-binaphthyl, 2,2′-dimethoxy, -3,3′-dicarbonylchloride, -3,3′-diacetylchloride and -3,3′-dipropanoylchloride. The epoxidation of styrene with the three iron catalysts, obtained after metalation of the free porphyrins, occurs with good yields and moderate ee up to 54%. These porphyrins showed unexpected conformational differences, as revealed by NMR spectroscopy. In particular, variable temperature NMR studies showed that the methoxy group in one of them undergoes intermediate conformational exchange on the ¹H NMR time scale at room temperature. Lowering the temperature to -50 °C revealed the presence of four states in slow exchange on the NMR time scale. These results evidence a dynamic conformational equilibrium of the binaphthyl handles that adopt different, asymmetric positions with respect to the porphyrin plane.

  通过将四-(α,β,α,β-2-氨基苯基)卟啉异构体与 1,1′-联萘、2,2′-二甲氧基、-3,3′-二羰酰氯、-3,3′-二乙酰氯和-3,3′-二丙酰氯缩合，制备了三种 "篮柄 "卟啉。游离卟啉金属化后，在三种铁催化剂的作用下，苯乙烯发生环氧化反应，产率高，ee值适中，最高可达 54%。核磁共振光谱显示，这些卟啉出现了意想不到的构象差异。特别是，变温核磁共振研究表明，其中一种卟啉中的甲氧基在室温下的 1H 核磁共振时间尺度上发生了中间构象交换。将温度降低到 -50 ℃ 时，核磁共振时间尺度上出现了四种缓慢交换状态。这些结果证明了二萘基手柄的动态构象平衡，它们相对于卟啉平面采用了不同的不对称位置。