| 1037589-94-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• CAS: 1037589-94-8
• 化学式: C₁₈H₂₁BrO₄Sn
• 分子量: 499.976
• InChiKey: PADRPFYZEFJAQU-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  在 copper(II) nitrate 作用下， 以 丙酮 为溶剂， 以13.6%的产率得到hexamethyl (5R,6S,11R,12S,17R,18S)-5,6,11,12,17,18-hexahydro-5,18:6,11:12,17-trimethanotrinaphthylene-2,3,8,9,14,15-hexacarboxylate
  参考文献：
  名称：

  Molecular Encapsulation via Metal-to-Ligand Coordination in a Cu(I)-Folded Molecular Basket

  摘要：

  A molecular basket, composed of a semirigid C-3 nu symmetric tris-norbornadiene framework and three pyridine flaps at the rim, has been shown to coordinate to a Cu(I) cation and thereby fold in a multivalent fashion. The assembly was effective (K-a = 1.73 +/- 0.08 x 10(5) M-1) and driven by enthalpy (Delta H degrees = -7.2 +/- 0.1 kcal/mol, Delta S degrees = -0.25 eu). Variable temperature H-1 NMR studies, assisted with 2D COSY and ROESY investigations, revealed the existence of Cu(I)-folded basket 10(b) with a molecule of acetonitrile occupying its interior and coordinated to the metal. Interestingly, 10(b) is in equilibrium with Cu(I)-folded 10(a), whose inner space is solvated by acetone or chloroform. The incorporation of a molecule of acetonitrile inside 10(a) was found to be driven by enthalpy (Delta H degrees = -3.3 +/- 0.1 kcal/mol), with an apparent loss in entropy (Delta S degrees= -9.4 +/- 0.4 eu); this is congruent with a complete immobilization of acetonitrile and release of a "loosely" encapsulated solvent molecule during 10(a/b) interconversion. From an Eyring plot, the activation enthalpy for incorporating acetonitrile into 10(a) was found to be positive (Delta H-double dagger = 6.5 +/- 0.5 kcal/mol), while the activation entropy was negative (Delta S-double dagger = -20 +/- 2 eu). The results are in agreement with an exchange mechanism whereby acetonitrile "slips" into an "empty" basket through its side aperture. In fact, DFT (BP86) calculations are in favor of such a mechanistic scenario; the calculations suggest that opening of the basket's rim to exchange guests is energetically demanding and therefore less feasible.

  DOI：

  10.1021/jo800748k

文献信息

• Stereo- and Regioselective Synthesis of Molecular Baskets
  作者：Michael J. Gunther、Radoslav Z. Pavlović、Joseph P. Fernandez、Lei Zhiquan、Judith Gallucci、Christopher M. Hadad、Jovica D. Badjić

  DOI：10.1021/acs.joc.9b00330

  日期：2019.4.5

  We describe a stereoselective method for obtaining multigram quantities of molecular basket 1syn in overall 11% yield, using inexpensive cyclopentadiene and diethyl fumarate as starting materials. First, an asymmetric synthesis of enantioenriched bromo(trimethylstannyl)alkene (−)-8 was accomplished by the stereoselective bromination of dibromonorbornene (+)-4 guided by anchimeric assistance and subsequent

  我们描述了一种立体选择方法，使用便宜的环戊二烯和富马酸二乙酯作为起始原料，可在总的11％的产率中获得多克数量的分子篮1 syn。首先，对映体富集的溴（三甲基锡烷基）烯烃（-）- 8的不对称合成是通过对二溴单降冰片烯（+）- 4的立体选择性溴化，并通过邻氨基苯甲酸协助进行的，随后顺式-外-消除四溴单降冰片烷（-）- 5a的。关键步骤。随后的Cu（I）催化的（-）- 8的环三聚反应被优化为1 syn / anti产率为85％，非对映异构体比例为1：1。重要的是，我们的机械实验结果与以链型方式与Cu（I）同手性二聚体中间体的外消旋作用发生的环三聚化相一致，从而降低了转化的立体选择性。通过更轻松地访问1型syn分子篮，可以完成一系列的识别研究，以生产新型超分子催化剂，有机磷清除剂和纳米结构材料。