(S)-3,3'-diethynyl-2,2'-bis(methoxymethoxy)-1,1'-binaphthyl

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (S)-3,3'-diethynyl-2,2'-bis(methoxymethoxy)-1,1'-binaphthyl
• 英文别名: 3-ethynyl-1-[3-ethynyl-2-(methoxymethoxy)naphthalen-1-yl]-2-(methoxymethoxy)naphthalene
• 化学式: C₂₈H₂₂O₄
• 分子量: 422.48
• InChiKey: WXRHWEBZTGVWPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-3,3'-diethynyl-2,2'-bis(methoxymethoxy)-1,1'-binaphthyl 在 盐酸 、 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 38.0h， 生成 (+)-(S,S,S)-tris[2,2'-dihydroxy-1,1'-binaphthalene-3,3'-diylbis(ethynyl)]
  参考文献：
  名称：

  Molecular Recognition of Pyranosides by a Family of Trimeric, 1,1′-Binaphthalene-Derived Cyclophane Receptors

  摘要：

  The synthesis and carbohydrale-recognition properties of a new family of optically active cyclophane receptors, 1-3, in which three 1,1'-binaphthalene-2,2'-diol spacers are interconnected by three bula-1,3-diynediyl linkers, are described. The macrocycles all contain highly preorganized cavities lined with six convergent OH groups for H-bonding and complementary in size and shape to monosaccharides. Compounds 1-3 differ by the functionality attached to the major groove of the 1,1'-binaphthalene-2.2'-diol spacers. The major grooves of the spacers in 2 are unsubstituted, whereas those in 1 bear benzyloxy (BnO) groups in the 7,7'-positions and those in 3 2-phenylethyl groups in the 6,6'-positions. The preparation of the more planar, D-3-symmetrical receptors (R,R,R)-1(Schemes I and 2), (S,S;S)-1 (Scheme 4), (S,S,S)-2 (Scheme 5), and (S,S,S)-3 (Scheme 8) involved as key step the Glaser-Hay cyclotrimerization of the corresponding OH-protected 3,3'-dielhynyl-1,1'-binaphthalene-2,2'-diol precursors, which yielded tetrameric and pentameric macrocycles in addition to the desired trimeric compounds. The synthesis of the less planar, C-2-symmetrical receptors (R,R,S)-2 (Scheme 6) and (S,S,R)-3 (Scheme 9) proceeded via two Glaser-Hay coupling steps. First, two monomeric precursors of identical configuration were oxidatively coupled to give a dimeric intermediate which was then subjected to macrocyclization with a third monomeric 1,1'-binaphthalene precursor of opposite configuration. The 3,3'-dialkynylation of the OH-protected 1,1'-binaphthalene-2,2'-diol precursors for the macrocyclizations was either performed by Stifle (Scheme I) or by Sonogashira (Schemes 4, 5, and 8) cross-coupling reactions. The flat D-3-symmetrical receptors (R,R,R)-1 and (S,S,S)-1 formed 1:1 cavity inclusion complexes with octyl 1-O-pyranosides in CDCl3 (300 K) with moderate stability (Delta G degrees ca. -3 kcal mol(-1)) as well as moderate diastereo(Delta(Delta G degrees) up to 0.7 kcal mol(-1)) and enantioselectivity (Delta(Delta G degrees) = 0.4 kcal mol(-1)) ( Table I). Stoichiometric 1 : 1 complexation by (S,S,S)-2 and (S,S,S)3 could not be investigated by H-1-NMR binding titrations, due to very strong signal broadening. This broadening of the H-1-NMR resonances is presumably indicative of higher-order associations, in which the planar macrocycles sandwich the carbohydrate guests. The less planar Ct-symmetrical receptor (S,S,R)-3 formed stable 1: 1 complexes with binding free enthalpies of up to Delta G degrees = - 5.0 kcal mol(-1) (Table 2). With diastereoselectivities up to Delta(Delta G degrees)=1.3 kcal mol(-1) and enantioselectivities of Delta(Delta G degrees)= 0.9 kcal mol(-1), (S,S,R)-3 is among the most selective artificial carbohydrate receptors known.

  DOI：

  10.1002/(sici)1522-2675(19981111)81:11<1931::aid-hlca1931>3.0.co;2-5
• 作为产物：
  描述：

  (S_a)-2,2'-bis(methoxymethoxy)-3,3'-bis[(trimethylsilyl)ethynyl]-1,1'-binaphthyl 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 (S)-3,3'-diethynyl-2,2'-bis(methoxymethoxy)-1,1'-binaphthyl
  参考文献：
  名称：

  自组装手性 FeII2L3 笼的合成与表征

  摘要：

  我们在此介绍了手性 BINOL 衍生的 (BINOL=1,1'-bi-2-naphthol) 双胺和双吡啶醛结构单元的合成，这些结构单元可用于新型手性 Fe II 2 L 3笼的自组装与铁(II)前体混合。通过核磁共振和圆二色性（CD）光谱、冷喷雾电离质谱和分子建模研究了一系列手性笼的性质。在形成 M 2 L 3笼时，铁角可以采用各种异构形式： mer 、 fac ‐Δ 或fac ‐Λ。我们发现， R-Cages 1和2中金属中心周围的配位几何形状仅在有限程度上受到手性BINOL主链的影响，因为在铁角处形成了具有fac和mer构型的笼的混合物。然而，通过使用双吡啶醛结构单元与手性胺部分结合生成这些手性 M 2 L 3笼，获得了对映体纯且高度对称的单一笼物种（ fac - RR - Cage和fac - RS - Cage ）形成吡啶亚胺配体以与铁配位。除了一致的 NMR 谱之外，CD 谱还

  DOI：

  10.1002/chem.201801077

文献信息

• Sonogashira Couplings Catalyzed by Fe Nanoparticles Containing ppm Levels of Reusable Pd, under Mild Aqueous Micellar Conditions
  作者：Sachin Handa、Bo Jin、Pranjal P. Bora、Ye Wang、Xiaohua Zhang、Fabrice Gallou、John Reilly、Bruce H. Lipshutz

  DOI：10.1021/acscatal.9b00007

  日期：2019.3.1

  Nanoparticles derived from FeCl3 containing the ligand XPhos and only 500 ppm Pd effect Sonogashira couplings in water between rt and 45 °C. The entire aqueous reaction medium can be easily recycled using an “in-flask” extraction. Several tandem processes in one pot are illustrated, including a sequence involving five steps (10 reactions) in good overall yield.

  含有配体XPhos和仅500 ppm Pd的FeCl 3衍生的纳米粒子在rt和45°C之间的水中会影响Sonogashira偶联。整个含水反应介质可以使用“烧瓶内”萃取法轻松回收。说明了一个罐中的几个串联过程，包括一个涉及五个步骤（10个反应）且总收率良好的序列。
• The Influence of Different Spacer Lengths on the Selectivity of Self-Assembly Processes of Bis(bipyridine)-BINOL Helicates
  作者：Jens Bunzen、Marko Hapke、Arne Lützen

  DOI：10.1002/ejoc.200900232

  日期：2009.8

  iron(II) or zinc(II) ions, however, a dramatic loss in the diastereoselectivity of the self-assembly of dinuclear triple-stranded helicates was observed as a result of increasing spacer length. In the case of zinc(II), the self-assembly processes were even found to be nonselective with regard to the composition of the helicates.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  报道了一系列对映体纯双（螯合）配体的合成和自组装行为。配体在 BINOL 核心和作为螯合实体的两个联吡啶基团之间的间隔单元中有所不同，并且发现配体经历完全非对映选择性自组装成具有银（I）盐的双核双链螺旋，如核磁共振和 CD 光谱和ESI 质谱。然而，在与铁 (II) 或锌 (II) 离子配位后，由于间隔长度增加，观察到双核三链螺旋自组装的非对映选择性显着丧失。在锌 (II) 的情况下，甚至发现自组装过程对螺旋体的组成是非选择性的。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Dendritic, 1,1′-Binaphthalene-Derived Cleft-Type Receptors (Dendroclefts) for the Molecular Recognition of Pyranosides
  作者：Anja Bähr、Béatrice Felber、Katharina Schneider、François Diederich

  DOI：10.1002/1522-2675(20000705)83:7<1346::aid-hlca1346>3.0.co;2-3

  日期：2000.7.5

  Two series of optically active, cleft-type dendritic receptors (dendroclefts) for carbohydrate recognition were prepared by attaching Frechet-type dendrons via ethynediyl linkers to a core consisting of one or two 1,1′-binaphthalene-2,2′-diyl phosphate moieties. Sugar substrates were expected to bind via bidentate ionic H-bonding of two OH groups to the phosphodiester core and, additionally, to undergo

  通过将 Frechet 型树突通过乙炔二基连接体连接到由一个或两个 1,1'-binaphthalene-2,2'-diyl phosphate 组成的核心上，制备了两个系列用于碳水化合物识别的光学活性裂隙型树突受体 (dendroclefts)部分。预计糖底物将通过两个 OH 基团的双齿离子 H 键与磷酸二酯核心结合，此外，与周围树枝状楔的芳香环发生范德华和 CH···π 相互作用。用单个联萘合成树突受体 G-1-(S)-1、G-2-(S)-2 和 G-3-(S)-3（图 1；Gx=树突生成）核心从 3,3'-二乙炔基化的 MOM 保护 (MOM=methoxymethyl) 1,1'-binaphthalene-2 开始，2'-二醇 (S)-13，第 1-3 代的 Frechet 型树突通过 Sonogashira 交叉偶联连接（方案 3）。MOM-醚脱保护，然后形成磷酸二酯和离子交换
• Preparation of Chiral Photosensitive Organocatalysts and Their Application for the Enantioselective Synthesis of 1,2-Diamines
  作者：Jiyuan Lyu、Aurélie Claraz、Maxime R. Vitale、Clémence Allain、Géraldine Masson

  DOI：10.1021/acs.joc.0c01931

  日期：2020.10.16

  Chiral phosphoric acid based organocatalysis and visible-light photocatalysis have both emerged as promising technologies for the sustainable production of fine chemicals. In this context, we have envisioned the design and the synthesis of a new class of chimeric catalytic entities that would feature both catalytic capabilities. Given their multitask nature, such catalysts would be particularly attractive

  基于手性磷酸的有机催化和可见光光催化都已成为可持续生产精细化学品的有前途的技术。在这种情况下，我们已经设想了设计和合成一类具有两种催化功能的新型嵌合催化实体。考虑到它们的多任务性质，这种催化剂对于开发新的催化转化特别是串联方法特别有吸引力。为了实现这一目标，已经制备并研究了具有一个或两个可见光敏感的噻吨酮部分的几个基于BINOL的手性磷酸骨架。这些新的光敏手性有机催化剂的效用随后在烯氨基甲酸酯的对映选择性串联三组分亲电胺化反应中得到证明。值得注意的是与呈现C 2对称性的那些相比，C 1对称性有机/光催化剂显示出更好的催化活性。
• Enantioselective Solid–Liquid Extraction of Native Saccharides with Chiral BINOL-Based Pyridine–Phenol Type Macrocycles
  作者：Yuki Ohishi、Mikino Murase、Hajime Abe、Masahiko Inouye

  DOI：10.1021/acs.orglett.9b01980

  日期：2019.8.16

  A chiral 1,1′-bi-2-naphthol (BINOL)-containing pyridine–acetylene–phenol macrocycle and a pyridine–BINOL alternating macrocycle were developed for enantioselective recognition of saccharides. In solid–liquid extraction of native saccharides, these macrocycles selectively extracted one enantiomer from each of a racemic mixture of d/l-fructose, d/l-glucose, and d/l-mannose into a lipophilic solvent.

  开发了一种手性的含1,1'-联-2-萘酚（BINOL）的吡啶-乙炔-苯酚大环和吡啶-BINOL交替大环用于对映体糖的识别。在固液提取天然糖的过程中，这些大环化合物从d / l-果糖，d / l-葡萄糖和d / l-甘露糖的外消旋混合物的每一种中选择性地提取一种对映异构体到亲脂性溶剂中。这是第一个实例，其中用人工宿主分子对映选择性地提取天然糖，尤其是重要的己糖。