(+)-(S,S,S)-tris[2,2'-bis(methoxymethoxy)-1,1'-binaphthalene-3,3'-diylbis(ethynyl)] | 219583-95-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: (+)-(S,S,S)-tris[2,2'-bis(methoxymethoxy)-1,1'-binaphthalene-3,3'-diylbis(ethynyl)]
• CAS: 219583-95-6；219617-22-8
• 化学式: C₈₄H₆₀O₁₂
• 分子量: 1261.39
• InChiKey: OJAOBAIRRJHPII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.08
• 重原子数：
  96.0
• 可旋转键数：
  18.0
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  110.76
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  (+)-(S,S,S)-tris[2,2'-bis(methoxymethoxy)-1,1'-binaphthalene-3,3'-diylbis(ethynyl)] 在 盐酸 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 12.0h， 以97%的产率得到(+)-(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 四甲基乙二胺 、 氧气 、 potassium carbonate 、 copper(l) chloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 29.0h， 生成 (+)-(S,S,S)-tris[2,2'-bis(methoxymethoxy)-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