(E)-penta-2,4-dienoyl azide | 65899-51-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-penta-2,4-dienoyl azide
• 英文别名: (2E)-2,4-pentadienoyl azide；(2E)-penta-2,4-dienoyl azide
• CAS: 65899-51-6
• 化学式: C₅H₅N₃O
• 分子量: 123.114
• InChiKey: DFSPAQTUJXUUMM-ONEGZZNKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-penta-2,4-dienoyl azide 以 甲苯 为溶剂， 反应 3.0h， 生成 (1E)-1-isocyanatobuta-1,3-diene
  参考文献：
  名称：

  Intramolecular Vinylation of Secondary and Tertiary Organolithiums

  摘要：

  Deprotonation of benzylic ureas, carbamates, and thiocarbamates bearing N'-alkenyl substituents generates carbanions which undergo intramolecular migration of the alkenyl group to the carbanionic center. Solvolysis of the urea products generates alpha-alkenylated amines. With an enantiomerically pure starting urea, migration proceeds stereospecifically, generating in enantiomerically enriched form products containing allylic quaternary stereogenic centers bearing N. Computational and in situ IR studies suggest that the reaction, formally a nucleophilic substitution at an sp(2) carbon atom, proceeds by a concerted addition-elimination pathway.

  DOI：

  10.1021/ja301591m
• 作为产物：
  描述：

  2,4-戊二烯酸 在 三乙胺 、 叠氮磷酸二苯酯 作用下， 反应 2.58h， 生成 (E)-penta-2,4-dienoyl azide
  参考文献：
  名称：

  手性吡啶鎓磷酰胺作为对布朗斯台德对偶-狄德尔-阿尔德反应的双重布朗斯台德酸催化剂

  摘要：

  手性吡啶鎓磷酰胺1·HX被设计为一类新型的手性布朗斯台德酸催化剂，其中吡啶电子质子和由吸电子吡啶鎓部分活化的相邻的酰亚胺样质子都可以作为强的双质子供体协同工作。1-氨基二烯与包括N-未取代的马来酰亚胺在内的各种亲二烯体的对映选择性Diels-Alder反应显示了1·HX的潜力，该反应尚未成功地用于不对称Diels-Alder反应。

  DOI：

  10.1021/acs.orglett.6b00608

文献信息

• Experimental Determination of the Absolute Enantioselectivity of an Antibody-Catalyzed Diels−Alder Reaction and Theoretical Explorations of the Origins of Stereoselectivity
  作者：Carina E. Cannizzaro、Jon A. Ashley、K. D. Janda、K. N. Houk

  DOI：10.1021/ja020879d

  日期：2003.3.1

  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.
• The enantioselective synthesis of tetracyclic methyllycaconitine analogues
  作者：Kevin Sparrow、David Barker、Margaret A. Brimble

  DOI：10.1016/j.tet.2011.08.026

  日期：2011.10

  A new enantioselective synthesis of ABEF ring analogues of methyllycaconitine has been developed using a chiral cobalt(III) salen-catalyzed Diels-Alder reaction to form the B ring. Subsequent elaboration to form the A, E and F rings was achieved by sequential Dieckmann, Mannich and Wacker-type cyclizations to afford tetracyclic analogues in 97.5% ee. (C) 2011 Elsevier Ltd. All rights reserved.
• Anti-Metallocene Antibodies: A New Approach to Enantioselective Catalysis of the Diels-Alder Reaction
  作者：Jari T. Yli-Kauhaluoma、Jon A. Ashley、Chih-Hung Lo、Lee Tucker、Mary M. Wolfe、Kim D. Janda

  DOI：10.1021/ja00132a001

  日期：1995.7

  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.
• Diels-Alder reactions of a surfactant 1,3-diene
  作者：David A. Jaeger、Hiraku Shinozaki、Patricia A. Goodson

  DOI：10.1021/jo00007a041

  日期：1991.3

  The ability of aqueous micelles and reversed micelles to control the regiochemistry of Diels-Alder reactions of (E,E)-6-[[[[4-[(4-hexylphenyl)sulfonyl]-1,3-butadienyl]amino] carbonyl]oxy]-N,N,N-trimethyl-1-hexanaminium bromide (4) and 1-(4-hexylphenyl)-2-propen-1-one (2b) was evaluated. If 2b and 4 were to react within the micelles in their preferred orientations, cycloadduct 10 would result, as opposed to 6-[[[[cis-6-(4-hexylbenzoyl)-cis-4-[(4-hexylphenyl)sulfonyl]-2-cyclohexen-1-yl]amino]carbonyl]oxy]-N,N,N-trimethyl-1-hexanaminium bromide (7b) and its exo isomer 8b, the theoretically predicted products actually obtained. The orientational effects in the aggregates were not strong enough to overcome the reaction's intrinsically preferred regiochemistry.
• Diastereoselective synthesis of a highly substituted cis-decahydroquinoline via a Knoevenagel condensation
  作者：Junfeng Huang、Stephen C. Bergmeier

  DOI：10.1016/j.tet.2008.04.073

  日期：2008.6

  A diastereoselective approach to 3,7,8-trisubstituted cis-decahydroquinolines is described. This ring system forms the core of rings B and E of the norditerpenoid alkaloid methyllycaconitine. This approach starts with a known disubstituted cyclohexene. The remaining carbons are attached via a Knoevenagel condensation followed by an intramolecular lactam formation. The stereochemistry of the substituents is controlled by the cis-substitution of the starting cyclohexene ring. (c) 2008 Elsevier Ltd. All rights reserved.