tert-butyl N-(2,2-dimethylpropylidene)carbamate | 1007216-85-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tert-butyl N-(2,2-dimethylpropylidene)carbamate
• CAS: 1007216-85-4
• 化学式: C₁₀H₁₉NO₂
• 分子量: 185.266
• InChiKey: WYIUBYCXSFFXSO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl N-(2,2-dimethylpropylidene)carbamate 、 2-(2-萘磺酰基)乙腈 在 (9H-fluoren-9-yl)methyl ((S)-1-(3-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)ureido)-2,2-dimethylpropyl)carbamate 、 三甲基氯硅烷 、 magnesium 、 1,2-二溴乙烷 作用下， 以 二氯甲烷 、 甲醇 为溶剂， 以77%的产率得到(S)-3-(N-tert-butoxycarbonylamine)-3-tert-butylpropanenitrile
  参考文献：
  名称：

  基于尿肽的布朗斯台德碱的设计，合成及在（对苯磺酰基）乙腈催化对映选择性合成β-氨基腈中的应用

  摘要：

  在亚胺上添加氰基烷基部分是制备β-氨基腈的一种非常有吸引力的方法。我们为立体选择性合成β-氨基腈提供了一种高效的有机催化方法，其中成功的关键是将基于尿素肽的布朗斯台德碱催化剂与（芳基磺酰基）乙腈结合使用作为乙腈阴离子的合成当量。该方法使人们能够以良好的收率和出色的对映选择性获得各种β-氨基腈，并拓宽了可用于合成的立体选择性曼尼希型方法。

  DOI：

  10.1002/chem.201304877

文献信息

• Lewis Base Catalyzed Aza-Diels-Alder Type Reactions between Danishefsky’s Dienes in the Presence of Lewis Base Catalysts. An Efficient Method for the Synthesis of Substituted 2,3-Dihydropyridin-4-ones
  作者：Takayuki Kitazawa、Yuji Maruyama、Teruaki Mukaiyama

  DOI：10.3987/com-07-s(u)65

  日期：——

  Aza-Diels-Alder type reactions of various imines with 1-methoxy-3-trimethylsilyloxy-1,3-butadiene (Danishefsky's diene) derivatives catalyzed by Lewis bases such as lithium methoxide are described. The reaction proceeds via a stepwise pathway, i.e. first by an imino-aldol reaction followed by the acid mediated annulation to afford the corresponding 2,3-dihydropyridin-4-ones in high yields. An appropriate

  描述了各种亚胺与 1-methoxy-3-trimethylsilyloxy-1,3-butadiene (Danishefsky's diene) 衍生物的 Aza-Diels-Alder 型反应，这些反应由 Lewis 碱如甲醇锂催化。该反应通过逐步途径进行，即首先通过亚氨基-羟醛反应，然后是酸介导的环化，以高产率提供相应的2,3-二氢吡啶-4-酮。An appropriate choice of the substituents on nitrogen plays important roles both in addition of the silyl enolates and in the subsequent annulation to form the desired cycloadducts.
• Highly Efficient Organosuperbase-Catalyzed Mannich-type Reactions of Sulfonylimidates with Imines: Successful Use of Aliphatic Imines as Substrates and a Unique Reaction Mechanism
  作者：Junya Nakano、Koichiro Masuda、Yasuhiro Yamashita、Shū Kobayashi

  DOI：10.1002/anie.201204572

  日期：2012.9.17

  First walk, then run! Highly efficient organosuperbase‐catalyzed Mannich‐type reactions of sulfonylimidates with readily prepared Boc‐protected imines have been developed. The desired products were obtained in high yield and with high anti selectivity. Mechanistic studies show an induction period for the catalyzed reaction, and that the organosuperbase works as an initiator.

  先走，再跑！已经开发出了高效的有机超碱催化的磺酰亚胺酯与易于制备的Boc保护的亚胺的曼尼希型反应。以高收率和高抗选择性获得所需产物。机理研究显示了催化反应的诱导期，并且有机超碱起了引发剂的作用。
• Catalytic Mannich-type reaction of phosphorylimidates
  作者：Shū Kobayashi、Junya Nakano、Ryosuke Matsubara

  DOI：10.1016/j.tet.2010.04.090

  日期：2010.8

  Phosphorylimidates reacted with N-Boc imines in the presence of a catalytic amount of potassium hexamethyldisilazide, to afford the corresponding Mannich-type adducts in high yields. It was shown that, like sulfonylimidates, phosphorylimidates can function as ester equivalents. In contrast to sulfonylimidates however, phosphorylimidates exhibited high anti-selectivity even in low polar solvents. An explanation for the anti-selectivity is given. (C) 2010 Elsevier Ltd. All rights reserved.