((2S,3S)-2-endo-3-phenylbicyclo[2.2.1]hept-5-en-2-yl)-(1-methyl-1H-imidazol-2-yl)methanone | 951291-07-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((2S,3S)-2-endo-3-phenylbicyclo[2.2.1]hept-5-en-2-yl)-(1-methyl-1H-imidazol-2-yl)methanone
• 英文别名: (1-methyl-1H-imidazol-2-yl)(-3-phenylbicyclo[2.2.1]hept-5-en-2-yl)methanone；(1-methylimidazol-2-yl)-[(1R,2S,3S,4S)-3-phenyl-2-bicyclo[2.2.1]hept-5-enyl]methanone
• CAS: 951291-07-9
• 化学式: C₁₈H₁₈N₂O
• 分子量: 278.354
• InChiKey: QUSHNOQNNUESIQ-UGUYLWEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲醇 、 ((2S,3S)-2-endo-3-phenylbicyclo[2.2.1]hept-5-en-2-yl)-(1-methyl-1H-imidazol-2-yl)methanone 在 4 A molecular sieve 、 三氟甲烷磺酸甲酯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 3.33h， 以41%的产率得到methyl (1R,2S,3S,4S)-3-phenylbicyclo[2.2.1]hept-5-ene-2-carboxylate
  参考文献：
  名称：

  α,β-Unsaturated 2-Acyl Imidazoles as a Practical Class of Dienophiles for the DNA-Based Catalytic Asymmetric Diels−Alder Reaction in Water

  摘要：

  alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic reaction was performed on a 1.0 mmol scale, and the imidazole auxiliary was removed readily.

  DOI：

  10.1021/ol7015274
• 作为产物：
  描述：

  1-(1-甲基-1H-咪唑-2-基)乙酮 在 Cu(4,4'-dimethyl-2,2'-bipyridyl)(NO₃)2 MOPS buffer 、 salmon testes DNA 作用下， 以 水 为溶剂， 反应 72.0h， 生成 ((2S,3S)-2-endo-3-phenylbicyclo[2.2.1]hept-5-en-2-yl)-(1-methyl-1H-imidazol-2-yl)methanone
  参考文献：
  名称：

  α,β-Unsaturated 2-Acyl Imidazoles as a Practical Class of Dienophiles for the DNA-Based Catalytic Asymmetric Diels−Alder Reaction in Water

  摘要：

  alpha,beta-Unsaturated 2-acyl imidazoles are a novel and practical class of dienophiles for the DNA-based catalytic asymmetric Diels-Alder reaction in water. The Diels-Alder products are obtained with very high diastereoselectivities and enantioselectivities in the range of 83-98%. The catalytic reaction was performed on a 1.0 mmol scale, and the imidazole auxiliary was removed readily.

  DOI：

  10.1021/ol7015274

文献信息

• Enantioselective CuII-Catalyzed Diels-Alder and Michael Addition Reactions in Water Using Bio-Inspired Triazacyclophane-Based Ligands
  作者：H. Bauke Albada、Fiora Rosati、David Coquière、Gerard Roelfes、Rob M. J. Liskamp

  DOI：10.1002/ejoc.201001522

  日期：2011.3

  triazacyclophane (TAC) scaffold decorated with three histidine amino acid residues was used as a tridentate ligand in asymmetric copper(II)-catalysed Diels–Alder and Michael addition reactions in water. Enantiomeric excesses up to 55 % were obtained in Diels–Alder reactions using ligands in which the histidine residues were directly attached to the TAC scaffold. Additional amino acid residues on the N-termini

  用三个组氨酸残基修饰的三氮杂环芳 (TAC) 支架用作不对称铜 (II) 催化的水中狄尔斯-阿尔德和迈克尔加成反应中的三齿配体。使用组氨酸残基直接连接到 TAC 支架上的配体在 Diels-Alder 反应中获得了高达 55% 的对映体过量。在组氨酸残基的 N 端或位于组氨酸残基和 TAC 支架之间的额外氨基酸残基导致对映选择性几乎完全丧失。对最特异性配体的配位复合物的建模研究表明，在催化活性中心附近存在底物结合袋。
• Ligand denticity controls enantiomeric preference in DNA-based asymmetric catalysis
  作者：Arnold J. Boersma、Bas de Bruin、Ben L. Feringa、Gerard Roelfes

  DOI：10.1039/c2cc17350f

  日期：——

  DNA-based catalysis can be used to control the enantioselectivity of copper-catalysed Diels-Alder and Friedel-Crafts reactions to produce either enantiomer of the product by changing the denticity of the ligand coordinated to the Cu(II) ion, even though the DNA adopts a right handed helical conformation only.

  基于DNA的催化可用于控制铜催化的Diels-Alder和Friedel-Crafts反应的对映选择性，以通过改变与Cu（II）离子配位的配体的密度来生成产物的任一对映体，即使DNA仅采用右手螺旋构型。
• Na+/K+ switch of enantioselectivity in G-quadruplex DNA-based catalysis
  作者：Changhao Wang、Guoqing Jia、Yinghao Li、Sufang Zhang、Can Li

  DOI：10.1039/c3cc45396k

  日期：——

  Here we found that the enantioselectivity of G-quadruplex DNA-based Diels-Alder reaction can be switched by just changing Na(+) to K(+), which is ascribed to the structural transformation of the G-quadruplex from antiparallel to hybrid-type. By tuning the ratio of Na(+)/K(+), the enantioselectivity of the Diels-Alder reaction could be switchable and shows much more sensitive to K(+) than to Na(+).

  在这里，我们发现，只需将Na（+）更改为K（+），即可切换基于G-四链体DNA的Diels-Alder反应的对映选择性，这归因于G-四链体从反平行到杂化-的结构转变。类型。通过调整Na（+）/ K（+）的比例，Diels-Alder反应的对映选择性可以切换，并且对K（+）的敏感性比对Na（+）的敏感性高得多。