2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl acetate | 740798-68-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl acetate
• 英文别名: (2,2-Dimethyl-5-nitroso-1,3-dioxan-5-yl) acetate
• CAS: 740798-68-9
• 化学式: C₈H₁₃NO₅
• 分子量: 203.195
• InChiKey: RCBWIRXTRSMVKE-UHFFFAOYSA-N

物化性质

• 沸点：
  247.7±40.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  74.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl acetate 生成 (E)-1,2-bis(5-acetoxy-2,2-dimethyl-1,3-dioxan-5-yl)diazene 1,2-dioxide
  参考文献：
  名称：

  α-Acyloxynitroso dienophiles in [4+2] hetero Diels–Alder cycloadditions: mechanistic insights

  摘要：

  alpha-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a beta-oxygenated moiety led to a domino [4+2] cycloaddition/sigma(N-O) bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the sigma(N-O) bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.02.065
• 作为产物：
  描述：

  (E)-1,2-bis(5-acetoxy-2,2-dimethyl-1,3-dioxan-5-yl)diazene 1,2-dioxide 以 二氯甲烷 为溶剂， 生成 2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl acetate
  参考文献：
  名称：

  α-Acyloxynitroso dienophiles in [4+2] hetero Diels–Alder cycloadditions: mechanistic insights

  摘要：

  alpha-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a beta-oxygenated moiety led to a domino [4+2] cycloaddition/sigma(N-O) bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the sigma(N-O) bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.02.065
• 作为试剂：
  描述：

  二碳酸二叔丁酯 、 1,3-环己二烯 在 2,2-dimethyl-5-nitroso-1,3-dioxan-5-yl acetate 、 盐酸 、 水 、 sodium hydroxide 作用下， 以 甲苯 、 水 为溶剂， 生成 tert-butyl 3-oxa-2-aza-bicyclo[2.2.2]oct-5-ene-2-carboxylate 、 tert-butyl (+/-)-(1S,4R)-(4-hydroxycyclohex-2-enyl)carbamate
  参考文献：
  名称：

  α-Acyloxynitroso dienophiles in [4+2] hetero Diels–Alder cycloadditions: mechanistic insights

  摘要：

  alpha-Acyloxynitroso derivatives are a class of heterodienophiles leading to valuable 3,6-dihydro-1,2-oxazines or the corresponding aminoalcohols in good yields. The discovery that a beta-oxygenated moiety led to a domino [4+2] cycloaddition/sigma(N-O) bond cleavage in the presence of a catalytic amount of Lewis acid was investigated in detail, through kinetic profiling of the reaction both in the absence and presence of a promoter. These studies showed that the role of the Lewis acid was to accelerate the sigma(N-O) bond cleavage thereby promoting a highly reproducible sequence. In addition, our preliminary results on an asymmetric version of this domino sequence are reported. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.02.065

文献信息

• Intermolecular nitroso Diels–Alder cycloaddition of α-acetoxynitroso derivatives in aqueous medium
  作者：Géraldine Calvet、Régis Guillot、Nicolas Blanchard、Cyrille Kouklovsky

  DOI：10.1039/b513397a

  日期：——

  The Diels-Alder cycloadditions of the alpha-acetoxynitroso dienophile in water are reported. The rapid and high yielding synthesis of structurally diverse 3,6-dihydro-1,2-oxazines complements the straightforward elaboration of aminoalcohols obtained from the alpha-acetoxynitroso derivative in anhydrous medium. A rationale for this solvent-dependent product distribution is proposed.

  报道了水中的α-乙酰氧基亚硝基二烯亲和物的Diels-Alder环加成反应。结构多样的3,6-二氢-1,2-恶嗪的快速高产合成补充了从α-乙酰氧基亚硝基衍生物在无水介质中获得的氨基醇的直接制备。提出了这种依赖溶剂的产物分布的原理。
• Lewis Acid-Promoted Hetero Diels−Alder Cycloaddition of α-Acetoxynitroso Dienophiles
  作者：Géraldine Calvet、Marion Dussaussois、Nicolas Blanchard、Cyrille Kouklovsky

  DOI：10.1021/ol0491336

  日期：2004.7.1

  [reaction: see text] alpha-Acetoxynitroso compound 3 has been prepared as a new stable, isolable, and reactive dienophile in nitroso Diels-Alder reactions. The yield of the [4 + 2] cycloaddition of alpha-acetoxynitroso dienophile with 1,3-dienes could be enhanced in the presence of 20 mol % Lewis acid. An unexpected retro hetero-Michael reaction from 26 was observed, leading to the cleavage of the

  [反应：见正文]在亚硝基Diels-Alder反应中，α-乙酰氧基亚硝基化合物3被制备为新的稳定，可分离和反应性的亲二烯体。在存在20mol％路易斯酸的情况下，可以提高α-乙酰氧基亚硝基二烯亲和体与1，3-二烯的[4 + 2]环加成的产率。观察到来自26的意外的逆杂迈克尔反应，导致环加合物的NO键断裂。该串联亚硝基Diels-Alder /复古异-迈克尔序列已与环状和非环状的1,3-二烯一起使用。