(S)-2-azidopropyl-2-methylcyclohexanone | 171737-77-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代酰胺
• 英文名称: (S)-2-azidopropyl-2-methylcyclohexanone
• 英文别名: (2S)-2-(3-azidopropyl)-2-methylcyclohexan-1-one
• CAS: 171737-77-2
• 化学式: C₁₀H₁₇N₃O
• 分子量: 195.264
• InChiKey: VTCTXAIYNASNII-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  (S)-2-azidopropyl-2-methylcyclohexanone 在 三氟乙酸 作用下， 生成 (S)-9a-Methyl-octahydro-pyrrolo[1,2-a]azepin-5-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
• 作为产物：
  描述：

  3-((S)-1-Methyl-2-oxo-cyclohexyl)-propionic acid ethyl ester 在 lithium aluminium tetrahydride 、 lithium tetrafluoroborate 、 三(2-氯乙基)胺 、 3 A molecular sieve 、 对甲苯磺酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙腈 、 苯 为溶剂， 反应 32.25h， 生成 (S)-2-azidopropyl-2-methylcyclohexanone
  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

• SYNTHESIS OF AN N-SUBSTITUTED LACTAM USING AN INTRAMOLECULAR SCHMIDT REACTION: FORMATION OF 2,3,11,11a-TETRAHYDRO-1H-BENZO[d]PYRROLO[1,2-a]AZEPIN-5(6H)-ONE
  作者：Grecian, Scott、Aubé, Jeff、Zhao, Dalian、Mathre, David J.

  DOI：10.15227/orgsyn.084.0347

  日期：——