dimethyl (1S,8R,9S,10S)-9-(benzenesulfonyl)-10-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl]oxytricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5-dicarboxylate | 1359820-82-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dimethyl (1S,8R,9S,10S)-9-(benzenesulfonyl)-10-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl]oxytricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5-dicarboxylate
• CAS: 1359820-82-8
• 化学式: C₃₁H₃₂O₁₀S
• 分子量: 596.655
• InChiKey: SUDODFUNEMQJGL-MWGYIBIISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  42
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  148
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  dimethyl (1S,8R,9S,10S)-9-(benzenesulfonyl)-10-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl]oxytricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5-dicarboxylate 在 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 potassium tert-butylate 、 水 、 碘 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 30.5h， 生成 dimethyl (1S,8R)-10-(hydroxymethyl)-11-azatetracyclo[6.5.1.02,7.09,13]tetradeca-2,4,6,9,12-pentaene-4,5-dicarboxylate
  参考文献：
  名称：

  Design, Preparation, and Study of Catalytic Gated Baskets

  摘要：

  We report a diastereoselective synthetic method to obtain a family catalytic molecular baskets containing a spacious cavity (similar to 570 angstrom(3)). These supramolecular catalysts were envisioned, via the process of gating, to control the access of substrates to the embedded catalytic center and thereby modulate the outcome of chemical reactions. In particular, gated basket 1 comprises a porphyrin "floor" fused to four phthalimide "side walls" each carrying a revolving aromatic "gate". With the assistance of H-1 NMR and UV-vis spectroscopy, we demonstrated that the small 1-methylimidazole guest (12, 94 angstrom(3)) would coordinate to the interior while the large' 1,5-diadamantylimidazole guest (14, 361 angstrom(3)) is relegated to tilt: exterior of basket Zn(II)-1. Subsequently, we examined the epoxidation of differently sized and shaped alkenes 18-21 with catalytic baskets 12(in)-Mn(III)-1 and 14(out)- Mn(III)-1 in the presence of the sacrificial oxidant iodosylarene. The epoxidation of cis-stilbene occurred in the cavity of 14(out)-, Mn(III)-1 and at the outer face of 12(in)Mn(III)-1 with the stereoselectivity of the two transformations being somewhat different. Importantly, catalytic basket 14(out)-Mn(III)-1 was capable of kinetically resolving an equimolar mixture of cis-2-octene 20 and cis-cyclooctene 21 via promotion of the transformation in its cavity.

  DOI：

  10.1021/jo202443j
• 作为产物：
  描述：

  dimethyl (1S,8R,9S,10S)-9-(benzenesulfonyl)-10-hydroxytricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5-dicarboxylate 、 (1S)-(-)-莰烷酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 dimethyl (1R,8S,9R,10R)-9-(benzenesulfonyl)-10-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl]oxytricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5-dicarboxylate 、 dimethyl (1S,8R,9S,10S)-9-(benzenesulfonyl)-10-[(1S,4R)-4,7,7-trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carbonyl]oxytricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5-dicarboxylate
  参考文献：
  名称：

  Design, Preparation, and Study of Catalytic Gated Baskets

  摘要：

  We report a diastereoselective synthetic method to obtain a family catalytic molecular baskets containing a spacious cavity (similar to 570 angstrom(3)). These supramolecular catalysts were envisioned, via the process of gating, to control the access of substrates to the embedded catalytic center and thereby modulate the outcome of chemical reactions. In particular, gated basket 1 comprises a porphyrin "floor" fused to four phthalimide "side walls" each carrying a revolving aromatic "gate". With the assistance of H-1 NMR and UV-vis spectroscopy, we demonstrated that the small 1-methylimidazole guest (12, 94 angstrom(3)) would coordinate to the interior while the large' 1,5-diadamantylimidazole guest (14, 361 angstrom(3)) is relegated to tilt: exterior of basket Zn(II)-1. Subsequently, we examined the epoxidation of differently sized and shaped alkenes 18-21 with catalytic baskets 12(in)-Mn(III)-1 and 14(out)- Mn(III)-1 in the presence of the sacrificial oxidant iodosylarene. The epoxidation of cis-stilbene occurred in the cavity of 14(out)-, Mn(III)-1 and at the outer face of 12(in)Mn(III)-1 with the stereoselectivity of the two transformations being somewhat different. Importantly, catalytic basket 14(out)-Mn(III)-1 was capable of kinetically resolving an equimolar mixture of cis-2-octene 20 and cis-cyclooctene 21 via promotion of the transformation in its cavity.

  DOI：

  10.1021/jo202443j

文献信息

• Design, Preparation, and Study of Catalytic Gated Baskets
  作者：Bao-Yu Wang、Teodora Žujović、Daniel A. Turner、Christopher M. Hadad、Jovica D. Badjić

  DOI：10.1021/jo202443j

  日期：2012.3.16

  We report a diastereoselective synthetic method to obtain a family catalytic molecular baskets containing a spacious cavity (similar to 570 angstrom(3)). These supramolecular catalysts were envisioned, via the process of gating, to control the access of substrates to the embedded catalytic center and thereby modulate the outcome of chemical reactions. In particular, gated basket 1 comprises a porphyrin "floor" fused to four phthalimide "side walls" each carrying a revolving aromatic "gate". With the assistance of H-1 NMR and UV-vis spectroscopy, we demonstrated that the small 1-methylimidazole guest (12, 94 angstrom(3)) would coordinate to the interior while the large' 1,5-diadamantylimidazole guest (14, 361 angstrom(3)) is relegated to tilt: exterior of basket Zn(II)-1. Subsequently, we examined the epoxidation of differently sized and shaped alkenes 18-21 with catalytic baskets 12(in)-Mn(III)-1 and 14(out)- Mn(III)-1 in the presence of the sacrificial oxidant iodosylarene. The epoxidation of cis-stilbene occurred in the cavity of 14(out)-, Mn(III)-1 and at the outer face of 12(in)Mn(III)-1 with the stereoselectivity of the two transformations being somewhat different. Importantly, catalytic basket 14(out)-Mn(III)-1 was capable of kinetically resolving an equimolar mixture of cis-2-octene 20 and cis-cyclooctene 21 via promotion of the transformation in its cavity.