Tert-butyl 1-benzyl-2-methylazetidine-2-carboxylate | 1269460-98-1

• 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: Tert-butyl 1-benzyl-2-methylazetidine-2-carboxylate
• CAS: 1269460-98-1
• 化学式: C₁₆H₂₃NO₂
• 分子量: 261.364
• InChiKey: VYELZFZHVXXJGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Tert-butyl 1-benzyl-2-methylazetidine-2-carboxylate 在 三氟乙酸 、 盐酸 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Practical preparation of enantiopure 2-methyl-azetidine-2-carboxylic acid; a γ-turn promoter

  摘要：

  A robust and practical synthesis of each enantiomer of 2-methyl-azetidine-2-carboxylic acid, based on the use of (S)-phenylglycinol as resolving agent, is described. This synthesis affords practical quantities of this quaternary amino acid suitably N- and C-protected for use in further peptide coupling. Synthetic highlights include the formation of the azetidine ring by intramolecular alkylation and the facile separation of the diastereoisomeric amides derived from phenylglycinol. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.05.006
• 作为产物：
  描述：

  2-溴丙酸叔丁酯 在 氯化亚砜 、 potassium tert-butylate 、 potassium carbonate 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 生成 Tert-butyl 1-benzyl-2-methylazetidine-2-carboxylate
  参考文献：
  名称：

  2-(1-羟基烷基)氮杂环丁烷扩环成4-(2-氯乙基)恶唑烷酮

  摘要：

  2-(1-羟基烷基)氮杂环丁烷在碱处理后与双(三氯甲基)碳酸酯(BTC)反应，得到4-(2-氯乙基)恶唑烷酮。详细检查了这种重排的范围，并且显示其效率取决于反应醇的类别和氮杂环丁烷环上的取代模式。

  DOI：

  10.1002/ejoc.201001375

文献信息

• The von Braun Reaction Applied to Azetidines
  作者：Karen Wright、Bruno Drouillat、Laurence Menguy、Jérôme Marrot、François Couty

  DOI：10.1002/ejoc.201701443

  日期：2017.12.22

  the reaction of cyanogen bromide with tertiary amines, was applied to a series of functionalized N-alkyl azetidines. This reaction mainly leads to the cleavage of the strained four-membered ring, producing 3-bromo N-alkyl cyanamides in good yield and variable regioselectivity, which can be used as original building blocks for the synthesis of nitrogen heterocycles.

  von Braun 反应，即溴化氰与叔胺的反应，应用于一系列功能化的 N-烷基氮杂环丁烷。该反应主要导致拉紧的四元环断裂，以良好的产率和可变的区域选择性产生 3-溴 N-烷基氰胺，可用作合成氮杂环的原始构件。
• Insight into the Regioselectivity of Nucleophilic Ring-Opening of Azetidinium Ions Containing Quaternary Carbon Atoms
  作者：Bruno Drouillat、Karen Wright、Olivier David、François Couty

  DOI：10.1002/ejoc.201200890

  日期：2012.10

  A set of azetidinium ions each bearing a quaternary carbon atom α to the nitrogen atom were synthesized. These compounds were treated with three different nuclophiles: azide, cyanide and acetate anions. Examination of the regioselectivity in the ring-opening reactions demonstrated that attack at the quaternary position is intrinsically favored over that at the secondary position. However, these SN2

  合成了一组氮杂环丁烷离子，每个离子在氮原子上带有一个季碳原子。这些化合物用三种不同的亲核试剂处理：叠氮化物、氰化物和乙酸根阴离子。对开环反应中的区域选择性的检查表明，四元位置的攻击本质上比第二位置的攻击更有利。然而，这些 SN2 反应对空间拥挤高度敏感，这可以抵消在季碳上反应的自然趋势。
• Synthesis of 2-Phenyl- and 2,2-Diarylpyrrolidines through Stevens Rearrangement Performed on Azetidinium Ions
  作者：Bruno Drouillat、Edouard d'Aboville、Flavien Bourdreux、François Couty

  DOI：10.1002/ejoc.201301536

  日期：2014.2

  atom either by a benzyl group or a benzhydryl group were synthesized to delineate the scope of their ring expansion into 2-phenyl- or 2,2-diaryl-pyrrolidines through a Stevens rearrangement. Whereas the regioselectivity of the rearrangement is very high, the diastereoselectivity is low when 2,3-disubstituted pyrrolidines are produced, except in one case. The major undesirable side-reaction is a Hofmann

  合成了一组在氮原子上被苄基或二苯甲基取代的氮杂环丁烷离子，以通过史蒂文斯重排描绘出它们扩环成 2-苯基-或 2,2-二芳基-吡咯烷的范围。尽管重排的区域选择性非常高，但在生成 2,3-二取代吡咯烷时，非对映选择性很低，但在一种情况下除外。主要的不希望有的副反应是导致环断裂的霍夫曼消除。
• Practical preparation of enantiopure 2-methyl-azetidine-2-carboxylic acid; a γ-turn promoter
  作者：Bruno Drouillat、Karen Wright、Jérôme Marrot、François Couty

  DOI：10.1016/j.tetasy.2012.05.006

  日期：2012.5

  A robust and practical synthesis of each enantiomer of 2-methyl-azetidine-2-carboxylic acid, based on the use of (S)-phenylglycinol as resolving agent, is described. This synthesis affords practical quantities of this quaternary amino acid suitably N- and C-protected for use in further peptide coupling. Synthetic highlights include the formation of the azetidine ring by intramolecular alkylation and the facile separation of the diastereoisomeric amides derived from phenylglycinol. (C) 2012 Elsevier Ltd. All rights reserved.
• Ring Expansion of 2-(1-Hydroxyalkyl)azetidines to 4-(2-Chloroethyl)oxazolidinones
  作者：François Couty、Bruno Drouillat、Frédéric Lemée

  DOI：10.1002/ejoc.201001375

  日期：2011.2

  2-(1-Hydroxyalkyl)azetidines react with bis(trichloromethyl) carbonate (BTC) after basic treatment to afford 4-(2-chloroethyl)oxazolidinones. The scope of this rearrangement was examined in detail and its efficiency was shown to depend on the class of the reacting alcohol and on the substitution pattern on the azetidine ring.

  2-(1-羟基烷基)氮杂环丁烷在碱处理后与双(三氯甲基)碳酸酯(BTC)反应，得到4-(2-氯乙基)恶唑烷酮。详细检查了这种重排的范围，并且显示其效率取决于反应醇的类别和氮杂环丁烷环上的取代模式。