(1E,3E)-4-(1',2',3',4'-tetra-O-acetyl-D-arabino-tetritol-1'-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene | 135181-67-8

• 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: (1E,3E)-4-(1',2',3',4'-tetra-O-acetyl-D-arabino-tetritol-1'-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene
• 英文别名: (1E,3E)-4-(tetra-O-acetyl-D-arabino-tetritol-1-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene；(1E,3E)-4-(tetra-O-acetyl-D-arabinotetritol-1-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene
• CAS: 135181-67-8
• 化学式: C₂₁H₂₆N₂O₉
• 分子量: 450.445
• InChiKey: GKUSUKODEVFPHM-PRQLOMMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.65
• 重原子数：
  32.0
• 可旋转键数：
  11.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  139.15
• 氢给体数：
  0.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  (1E,3E)-4-(1',2',3',4'-tetra-O-acetyl-D-arabino-tetritol-1'-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene 以 氯仿 为溶剂， 反应 120.0h， 生成 (6S,4E)-4-(2',3',4'-tri-O-acetyl-1'-deoxy-D-erythritol-1'-ylidene)-6-cyano-1-(4-methoxyphenyl)-1,4,5,6-tetrahydropyridazine
  参考文献：
  名称：

  关于基于碳水化合物的1,2-二氮杂-1,3-丁二烯和丙烯腈的环加成反应的实验和理论见解。手性偶氮烯烃和不对称烯烃行为的模型案例。

  摘要：

  通过手性1,2-二氮杂-1,3-丁二烯1和2与丙烯腈的杂Diels-Alder反应制备了一系列基于碳水化合物的四氢哒嗪。反应是区域特异性的，并且观察到的非对映选择性与对异二烯单元的Re面的优选攻击相一致，因为置于C4的手性糖确实在很大程度上保护了相反的Si面。通过X射线晶体学研究已经牢固地确定了主要环加合物4的立体化学，该X射线晶体学研究还揭示了将氰基置于轴向的构象。其中轴向氰基和碳水化合物部分呈顺式关系的9类和11类负载物经历了轻松的E2消除，从而消除了空间拥堵。据报道，进行了详细的计算研究，以更好地了解影响这种不对称环加成的因素。在简化模型上进行的DFT研究（B3LYP / 6-31G）可以正确预测实验观察到的区域化学反应，而面部非选择性选择是在母体试剂的半经验（PM3）水平上建模的，因此可以说明手性化合物提供的空间因子取代基。该计算还表明，就稳定的异头作用而言，氰基的轴向取向可以合理

  DOI：

  10.1021/jo016266l
• 作为产物：
  描述：

  (3E)-4-(tetra-O-acetyl-D-arabinotetritol-1-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene 以 苯 为溶剂， 生成 (1E,3E)-4-(1',2',3',4'-tetra-O-acetyl-D-arabino-tetritol-1'-yl)-1-(4-methoxyphenyl)-1,2-diaza-1,3-butadiene
  参考文献：
  名称：

  手性糖偶氮烯烃的热和光化学转换：机械询问。

  摘要：

  将光不稳定的偶氮基团掺入不饱和糖链中，可得到一类在温和条件下（阳光照射）易受热和光诱导转换影响的糖模拟物。在本文中，通过实验和DFT计算来解开这种立体变异和机理路线。

  DOI：

  10.1002/ejoc.202000029

文献信息

• Diastereofacial selectivity in diels-alder reactions of chiral 1,2-diaza-1,3-butadienes from carbohydrates
  作者：M. Avalos、R. Babiano、P. Cintas、J.L. Jiménez、M.M. Molina、Palacios J.C、J.B. Sánchez

  DOI：10.1016/s0040-4039(00)74369-3

  日期：1991.11

  The synthesis of several 1,2-diaza-1,3-butadienes 1 derived from carbohydrates is described. The reaction of 1, as chiral dienophiles, with 1,4-benzoquinone, 1,4-napthoquinone, and diethyl azodicarboxylate ocurs with high ν-facial stereoselectivity.

  描述了衍生自碳水化合物的几种1,2-二氮杂-1,3-丁二烯1的合成。的反应1，手性亲双烯体，用1,4-苯醌，1,4-萘醌，和具有高ν面部立体选择性偶氮二甲酸二乙酯ocurs。
• Hetero-Diels−Alder Reactions of Homochiral 1,2-Diaza-1,3-butadienes with Diethyl Azodicarboxylate under Microwave Irradiation. Theoretical Rationale of the Stereochemical Outcome
  作者：Martín Avalos、Reyes Babiano、Pedro Cintas、Fernando R. Clemente、José L. Jiménez、Juan C. Palacios、Juan B. Sánchez

  DOI：10.1021/jo990442x

  日期：1999.8.1

  The stereoselective normal electron demand Dials-Alder reactions of chiral 1,2-diaza-1,3-butadienes, derived from acyclic carbohydrates having different configurations (1-6), with diethyl azodicarboxylate (DEAD) are disclosed. Reactions proceed slowly in benzene solution at room temperature, but are greatly accelerated by microwave irradiation to form the corresponding functionalized 1,2,3,6-tetrahydro-1,2,3,4-tetrazines (7-18) in good yields. The observed stereoselectivity is markedly dependent on the relative stereochemistry at C-1',2'. Thus, 1,2-diazoalkenes derived from per-O-acylated sugars having three configuration at C-1',2' give tetrazines with a high facial selectivity, whereas those having erythro configuration at C-1',2' afford products in lower diastereomeric ratios. The facial diastereoselection has been rationalized by a PM3 computational study. These results prove that in the transition structures (TSs) the reacting azoalkene exhibits formal negative charges at C-3 and N-2, the former being of greater magnitude, while the heterodienophile displays a partial positive charge at the substituent attached to the nitrogen atom. Accordingly, a stabilizing electrostatic interaction will only occur in TSs involving an endo orientation of the azodicarboxylate in its approach to the azadiene, a fact consistent with the experimental observations.
• Diastereoselective Cycloadditions of 1,3-Thiazolium-4-olates with Chiral 1,2-Diaza-1,3-butadienes
  作者：Martín Avalos、Reyes Babiano、Pedro Cintas、Fernando R. Clemente、Ruth Gordillo、José L. Jiménez、Juan C. Palacios、Paul R. Raithby

  DOI：10.1021/jo991841v

  日期：2000.8.1

  A series of 2-(N-methyl)benzylamino-1,3-thiazolium-4-olates (2-aminothioisomunchnones) react with chiral 1,2-diaza-1,3-butadienes derived from carbohydrates to afford a diastereomeric mixture of (4R,5S)- and (4R,5R)-4,5-dihydrothiophenes. These substrate-controlled cycloadditions are chemoselective, regiospecific, and proceed with a high facial diastereoselection. A theoretical rationale at semiempirical level does justify the stereochemical outcome observed in the experiments.
• A facile and expeditious entry to acyclic carbohydrate-derived 1,2-diazabutadienes
  作者：Martín Avalos、Reyes Babiano、Pedro Cintas、JoséL. Jiménez、Juan C. Palacios、Juan B. Sánchez

  DOI：10.1016/0957-4166(95)00104-w

  日期：1995.4

  Chiral 1,2-diaza-1,3-butadienes derived from acyclic monosaccharides are easily prepared from the corresponding and readily available unprotected sugars in a two-step sequence.