4-(methoxycarbonyl)benzyl trans-1,3-butadiene-1-carbamate | 152839-68-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(methoxycarbonyl)benzyl trans-1,3-butadiene-1-carbamate
• 英文别名: p-methoxycarbonylbenzyl trans-1,3-butadiene-1-carbamate；methyl 4-[[(1E)-buta-1,3-dienyl]carbamoyloxymethyl]benzoate
• CAS: 152839-68-4
• 化学式: C₁₄H₁₅NO₄
• 分子量: 261.277
• InChiKey: XSRQTSWSJDUHOP-RUDMXATFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-(methoxycarbonyl)benzyl trans-1,3-butadiene-1-carbamate 在 lithium hydroxide 、 对叔丁基邻苯二酚 、 双氧水 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 74.0h， 生成 (3S,4S)-3-(N'-p-methoxycarbonylbenzyloxycarbonylamino)-1-cyclohexene-4-carboxylic acid
  参考文献：
  名称：

  Experimental Determination of the Absolute Enantioselectivity of an Antibody-Catalyzed Diels−Alder Reaction and Theoretical Explorations of the Origins of Stereoselectivity

  摘要：

  The exo and endo Diels-Alder adducts of p-methoxycarbonylbenzyl trans-1,3-butadiene- 1 carbamate and N,N-dimethylacrylamide have been synthesized, and the absolute configurations of resolved enantiomers have been determined. On the basis of this information, the absolute enantioselectivities of the Diels-Alder reaction catalyzed by antibodies 13G5 and 4D5 as well as other catalytic antibodies elicited in the same immunizations have been established. The effects of different arrangements of catalytic residues on the structure and energetics of the possible Diels-Alder transition states were modeled quantum mechanically at the B3LYP/6-311++G**//B3LYP/6-31+G** level of theory. Flexible docking of these enantiomeric transition states in the antibody active site followed by molecular dynamics on the resulting complexes provided a prediction of the transition-state binding modes and an explanation of the origin of the observed enantioselectivity of antibody 13G5.

  DOI：

  10.1021/ja020879d
• 作为产物：
  描述：

  4-(羟甲基)苯甲酸甲酯 、 (E)-penta-2,4-dienoyl azide 以 甲苯 为溶剂， 反应 0.67h， 生成 4-(methoxycarbonyl)benzyl trans-1,3-butadiene-1-carbamate
  参考文献：
  名称：

  Anti-Metallocene Antibodies: A New Approach to Enantioselective Catalysis of the Diels-Alder Reaction

  摘要：

  We have shown how a constrained bicyclo[2.2.2]octene hapten can elicit antibody catalysts for the Diels-Alder reaction between 4-carboxybenzyl trans-1,3-butadiene-1-carbamate and N,N-dimethylacrylamide (Gouverneur, V. E,; de Pascual-Teresa, B.; Beno, B.; Janda, K. D.; Lerner, R. A. Science 1993, 262, 204). In the present study we have developed a new approach to hapten design for elicitation of Diels-Alder catalytic antibodies. Our strategy was to engage the freely rotating eta(5)-cyclopentadienyl iron complex as the haptenic group. By applying such a flexible hapten we set out to determine if the immune system could freeze out a conformer which mimics the Diels-Alder transition state and hence produce new Diels-Alderases. If so, how would the catalytic rates, diastereo- and enantioselectivity of these antibodies compare with those of antibodies elicited by the former methodology? We generated antibodies that catalyzed the Diels-Alder reaction with high enantio- and diastereoselectivity and had effective molarities (EM) comparable to those of antibodies elicited using the constrained bicyclo[2.2.2]octene haptens. This methodology offers a new approach to the production of antibodies for the catalysis of other reactions with pericyclic, highly-ordered transition states.

  DOI：

  10.1021/ja00132a001