2-(3-Azidopropyl)-2-methylcyclobutan-1-one | 148028-73-3

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: 2-(3-Azidopropyl)-2-methylcyclobutan-1-one
• CAS: 148028-73-3
• 化学式: C₈H₁₃N₃O
• 分子量: 167.211
• InChiKey: JDBNFQSJLWTCPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(3-Azidopropyl)-2-methylcyclobutan-1-one 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 4.0h， 以96%的产率得到5-Methyl-azocan-2-one
  参考文献：
  名称：

  Highly efficient intramolecular addition of aminyl radicals to carbonyl groups: a new ring expansion reaction leading to lactams

  摘要：

  DOI：

  10.1021/ja00061a041
• 作为产物：
  描述：

  cyclopropyldiphenylsulfonium tetrafluoroborate 、 5-叠氮戊烷-2-酮 在 氢氧化钾 作用下， 以 二甲基亚砜 为溶剂， 反应 1.5h， 生成 2-(3-Azidopropyl)-2-methylcyclobutan-1-one
  参考文献：
  名称：

  Intramolecular Schmidt Reactions of Alkyl Azides with Ketones: Scope and Stereochemical Studies

  摘要：

  The intramolecular Schmidt reaction of alkyl azides and ketones has been demonstrated. The reaction is proposed to occur via initial attack of an azide on a ketone activated by a variety of protic or Lewis acids, including trifluoroacetic acid, titanium tetrachloride, and others. The resulting azidohydrin undergoes a direct rearrangement to afford the product amide and molecular nitrogen. When cyclic ketones are used, fused bicyclic lactams of types encountered in a wide variety of natural products are obtained. Although the distance allowed between the carbonyl group and the alkyl azide is quite restricted, the reaction is general with respect to the ketone component, including acyclic ketones and cyclic substrates ranging from standard to large ring sizes. The reaction also succeeds with aldehydes, although elimination or hydride migration products compete. In several cases examined, the reaction was found to proceed with retention of configuration at the migrating carbon. Competing reactions with beta-diketones and alpha,beta-unsaturated ketones were found to predominate over ring expansion.

  DOI：

  10.1021/ja00147a006

文献信息

• Intramolecular Schmidt reactions of alkyl azides with ketals and enol ethers
  作者：Craig J. Mossman、Jeffrey Aubé

  DOI：10.1016/0040-4020(96)00037-3

  日期：1996.3

  The ketals or enol ethers of 1,5-azidoketones were converted into lactams using a two-stage process. Treatment of the ketals and enol ethers with acid (trifluoroacetic acid, triflic acid, or trimethylsilyl triflate) afforded an oxonium ion which reacted with the tethered azide to give a 1,1-azido-alkoxy intermediate. Bond reorganization led to an iminium ether that was reacted with sodium iodide in

  使用两步法将1，5-叠氮酮的缩酮或烯醇醚转化为内酰胺。用酸（三氟乙酸，三氟甲磺酸或三甲基三氟甲磺酸酯）处理缩酮和烯醇醚，得到氧鎓离子，其与束缚的叠氮化物反应，得到1，1-叠氮基-烷氧基中间体。键的重组产生了亚胺醚，该亚胺醚与碘化钠在丙酮中反应以暴露出酰胺产物。据报道，使用二甲基或二乙基缩酮，有七个分子内实例的收率在68％至≥95％之间。还描述了使用1，3-二氧戊环的尝试和一个分子间的实例。
• Intramolecular Schmidt reaction of alkyl azides
  作者：Jeffrey Aube、Gregory L. Milligan

  DOI：10.1021/ja00023a065

  日期：1991.11
• Intramolecular Schmidt Reactions of Alkyl Azides with Ketones: Scope and Stereochemical Studies
  作者：Gregory L. Milligan、Craig J. Mossman、Jeffrey Aube

  DOI：10.1021/ja00147a006

  日期：1995.10

  The intramolecular Schmidt reaction of alkyl azides and ketones has been demonstrated. The reaction is proposed to occur via initial attack of an azide on a ketone activated by a variety of protic or Lewis acids, including trifluoroacetic acid, titanium tetrachloride, and others. The resulting azidohydrin undergoes a direct rearrangement to afford the product amide and molecular nitrogen. When cyclic ketones are used, fused bicyclic lactams of types encountered in a wide variety of natural products are obtained. Although the distance allowed between the carbonyl group and the alkyl azide is quite restricted, the reaction is general with respect to the ketone component, including acyclic ketones and cyclic substrates ranging from standard to large ring sizes. The reaction also succeeds with aldehydes, although elimination or hydride migration products compete. In several cases examined, the reaction was found to proceed with retention of configuration at the migrating carbon. Competing reactions with beta-diketones and alpha,beta-unsaturated ketones were found to predominate over ring expansion.
• Highly efficient intramolecular addition of aminyl radicals to carbonyl groups: a new ring expansion reaction leading to lactams
  作者：Sunggak Kim、Goon Ho Joe、Jung Yun Do

  DOI：10.1021/ja00061a041

  日期：1993.4