2-(3'-azidopropyl)-cyclohex-2-en-1-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(3'-azidopropyl)-cyclohex-2-en-1-one
• 英文别名: 2-(3-azidopropyl)cyclohex-2-en-1-one；2-(3'-azidopropyl)cyclohex-2-enone
• 化学式: C₉H₁₃N₃O
• 分子量: 179.222
• InChiKey: SIJGJWAHKOFUGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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)-cyclohex-2-en-1-one 在 咪唑 、 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 、 sodium acetate 、 四氯化钛 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 正戊烷 、 苯 为溶剂， 反应 22.5h， 生成 9a-Allyl-hexahydro-pyrrolo[1,2-a]azepine-5,9-dione
  参考文献：
  名称：

  串联半松果酚/施密特反应导致了一种多用途和高效的方法来处理四氮杂生物碱骨架。

  摘要：

  [结构：见正文]设计并开发了TiCl4促进的串联半松果酚/奥伯型α-甲硅烷氧基-环氧叠氮化物的分子内Schmidt反应，是有效构建氮杂季碳单元的通用方法。作为适用的例子，已经构建了掺入许多重要生物碱中的一些关键的三环氮杂四价骨架，例如头孢他辛，塞莫胺，赤藓醇和高赤藓醇生物碱。

  DOI：

  10.1021/ol062116r
• 作为产物：
  描述：

  2-(3'-chloropropyl)cyclohex-2-enone 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 以61%的产率得到2-(3'-azidopropyl)-cyclohex-2-en-1-one
  参考文献：
  名称：

  使用多米诺反应一锅法合成内酰胺：施密特反应与樱井和羟醛反应的组合

  摘要：

  报道了一系列多米诺反应，其中分子内施密特反应与樱井反应、羟醛反应或两者结合。烯丙基硅烷与含叠氮基烯酮在路易斯酸性条件下的 Sakurai 反应，然后是所得钛烯醇化物物质的质子化，允许随后的分子内施密特反应。或者，中间体钛烯醇化物可以进行羟醛反应，然后进行分子内施密特反应，形成具有多个立体中心的内酰胺产物。讨论了在多米诺骨牌过程中钛烯醇醛醇反应与几种 3-叠氮醛底物的立体化学特征。

  DOI：

  10.1021/jo901843w

文献信息

• Probing chemical space with alkaloid-inspired libraries
  作者：Michael C. McLeod、Gurpreet Singh、James N. Plampin、Digamber Rane、Jenna L. Wang、Victor W. Day、Jeffrey Aubé

  DOI：10.1038/nchem.1844

  日期：2014.2

  Screening of small-molecule libraries is an important aspect of probe and drug discovery science. Numerous authors have suggested that bioactive natural products are attractive starting points for such libraries because of their structural complexity and sp3-rich character. Here, we describe the construction of a screening library based on representative members of four families of biologically active

  小分子文库的筛选是探针和药物发现科学的一个重要方面。许多作者认为生物活性天然产物是此类文库的有吸引力的起点，因为它们的结构复杂性和sp 3-丰富的性格。在这里，我们描述了基于生物活性生物碱的四个家族（百合科、结构相关的环菱碱和lepadiformine 家族、羽扇豆和石蒜科）的代表性成员的筛选库的构建。在每种情况下，支架都是基于天然存在的化合物或近似衍生物的结构。在开发出合适的化学方法之后进行了支架制备。多样化提供了 686 种适合筛选的新化合物。如此制备的文库具有结构特征，包括sp 3含量，可与代表性天然产物的基础组相媲美，并且高度符合五规则。
• An Efficient Total Synthesis of (±)-Stemonamine
  作者：Yu-Ming Zhao、Peiming Gu、Yong-Qiang Tu、Chun-An Fan、Qingwei Zhang

  DOI：10.1021/ol800433r

  日期：2008.5.1

  An efficient first approach to the Stemona alkaloid (+/-)-Stemonamine has been developed on the basis of a key TiCl4 promoted tandem Semipinacol rearrangement/Schmidt reaction and a Dieckmann condensation reaction.
• Domino Reactions That Combine an Azido-Schmidt Ring Expansion with the Diels−Alder Reaction
  作者：Yibin Zeng、D. Srinivasa Reddy、Erin Hirt、Jeffrey Aubé

  DOI：10.1021/ol047809r

  日期：2004.12.1

  The combination of the intramolecular Schmidt reaction with the Diels-Alder reaction provides expedient access to a variety of heterocycles. Two different modes of reaction planning are presented. In one, the azide and ketone moieties necessary for the intramolecular Schmidt reaction originate on different molecules that are reacted and subsequently undergo a ring-adjustment step. Alternatively, an azido ketone can be used provided the ketone is deactivated by its presence in an enone.
• 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.
• Thermal rearrangements of α-(ω-azidoalkyl) enones
  作者：Gary A. Molander、Christopher T. Bibeau

  DOI：10.1016/s0040-4039(02)01077-8

  日期：2002.7

  The thermal rearrangement of alpha-(omega-azidoalkyl) enones has been investigated. A variety of these substrates were synthesized and subjected to thermal rearrangement to investigate the scope and generality of their transformation to bicyclic lactams. (C) 2002 Elsevier Science Ltd. All rights reserved.