2-Naphthalenol, 3-iodo-7-(phenylmethoxy)- | 219481-43-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2-Naphthalenol, 3-iodo-7-(phenylmethoxy)-
• 英文别名: 7-Benzyloxy-3-iodo-naphthalen-2-ol
• CAS: 219481-43-3
• 化学式: C₁₇H₁₃IO₂
• 分子量: 376.194
• InChiKey: OLUHLWYTMVGFBB-UHFFFAOYSA-N

物化性质

• 沸点：
  453.4±30.0 °C(Predicted)
• 密度：
  1.644±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.73
• 重原子数：
  20.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-Naphthalenol, 3-iodo-7-(phenylmethoxy)- 在 叔丁胺 、 copper dichloride 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以65%的产率得到7,7'-Bis-benzyloxy-3,3'-diiodo-[1,1']binaphthalenyl-2,2'-diol
  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：

  6-bromo-7-(methoxymethoxy)naphthalen-2-ol 在 盐酸 、 碘 、 叔丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 、 正戊烷 为溶剂， 反应 16.5h， 生成 2-Naphthalenol, 3-iodo-7-(phenylmethoxy)-
  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

文献信息

• Optically Active Cyclophane Receptors for Mono- and Disaccharides: The Role of Bidentate Ionic Hydrogen Bonding in Carbohydrate Recognition
  作者：Anne Sophie Droz、Ulf Neidlein、Sally Anderson、Paul Seiler、François Diederich

  DOI：10.1002/1522-2675(20010815)84:8<2243::aid-hlca2243>3.0.co;2-g

  日期：2001.8.15

  feature very different molecular shapes (Fig. 10). In 1H-NMR binding titrations with mono- and disaccharides (Fig. 13), concentration ranges were chosen to favor 1 : 1 host−guest binding. This stoichiometry was experimentally established by the curve-fitting analysis of the titration data and by Job plots. The titration data demonstrate conclusively that the strength of carbohydrate recognition is enhanced

  描述了一种新的旋光环烷受体家族，用于在竞争性质子溶剂混合物中络合单糖和二糖。大环化合物 (−)-(R,R,R,R)-1 – 4 具有由四个 1,1'-binaphthalene-2,2'-磷酸二酯部分通过桥接在 3,3'-位置形成的预组织结合腔炔属或苯炔属间隔物。四个磷酸二酯基团向结合腔汇聚并提供有效的双齿离子 H 键受体位点（图 2）。1,1'-联萘部分的 7,7'-位上的苄氧基确保纳米尺寸受体的溶解性并防止不希望的聚集。四种环烷的大环框架的构建利用了 Sonogashira 协议的 Pd0 催化的芳基 - 乙炔交叉偶联，和氧化炔属均偶联方法（方案 2 和 8 – 10）。还制备了几种具有一个 1,1'-联萘-2,2'-磷酸二酯部分的裂隙型受体（方案 1、6 和 7）。在目标化合物的合成过程中遇到的一个不希望的副反应是通过 5-endo-dig 环化从 3-ethynylnaphthalene-2-ol