2-(3-azidopropyl)-2-methyl-1,3-cyclohexanedione | 911213-97-3

• 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-methyl-1,3-cyclohexanedione
• 英文别名: 2-(3-azidopropyl)-2-methylcyclohexane-1,3-dione；2-(3-Azidopropyl)-2-methylcyclohexane-1,3-dione
• CAS: 911213-97-3
• 化学式: C₁₀H₁₅N₃O₂
• 分子量: 209.248
• InChiKey: FONGOUOBALDRCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  48.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(3-azidopropyl)-2-methyl-1,3-cyclohexanedione 在 甲基三氧化铼(VII) 4-二甲氨基吡啶 、 三乙胺 作用下， 以 乙醚 、 1,2-二氯乙烷 为溶剂， 反应 4.0h， 生成 1-acetyl-4a-methyl-2,3,4,4a,6,7-hexahydro-1H-quinolin-5-one
  参考文献：
  名称：

  Synthesis and Application of P-Stereogenic Phosphines as Superior Reagents in the Asymmetric Aza-Wittig Reaction

  摘要：

  [GRAPHICS]A wide variety of P-stereogenic aryldialkylphosphines were prepared in enantioenriched form by a systematic diversification of the (-)-sparteine-mediated dynamic kinetic resolution of racemic lithiophosphine-boranes reported by Livinghouse. Excellent asymmetric induction was observed provided that the intermediate lithiophosphine/sparteine complex precipitated from solution; more soluble derivatives returned poor ee's or racemic material. The resulting phosphine-boranes were deprotected and used as reagents in the desymmetrizing asymmetric aza-Wittig reaction of 2-alkyl-2-(3-azidopropyl)cyclohexane-1,3-diones, delivering the highest ee's yet observed in this process (up to 84% ee). Phosphines bearing bulky substituents required heating for the aza-Wittig reaction to proceed to completion, which P-31 NMR studies showed to be due to interception of the reaction by the formation of unreactive (E)-phosphazides. This was circumvented by use of methyltrioxorhenium to catalyze the formation of iminophosphoranes from the azide and phosphine, allowing reactions to take place at ambient temperature, although the ee's of the asymmetric reactions were reduced in these examples.

  DOI：

  10.1021/jo0709908
• 作为产物：
  描述：

  2-allyl-2-methyl-1,3-cyclohexanedione 在 bis(cyclohexanyl)borane 、 碘 、 sodium acetate 、 sodium azide 、 四丁基碘化铵 作用下， 以 四氢呋喃 、 水 、 丙酮 为溶剂， 生成 2-(3-azidopropyl)-2-methyl-1,3-cyclohexanedione
  参考文献：
  名称：

  不对称的氮杂-维蒂希反应：β-季氮杂环的对映选择性合成。

  摘要：

  DOI：

  10.1002/anie.200601383

文献信息

• Concise access to indolizidine and pyrroloazepine skeleta via intramolecular Schmidt reactions of azido 1,3-diketones
  作者：Duanpen Lertpibulpanya、Stephen P. Marsden

  DOI：10.1039/b608801e

  日期：——

  Readily prepared 2-alkyl-2-azidopropylcycloalkyl-1,3-diones undergo intramolecular Schmidt rearrangement with a range of hard Lewis acids, leading to indolizidinediones and pyrroloazepinediones. Chiral aluminium-based Lewis acids could also be used to mediate this symmetry-breaking transformation, but no significant asymmetric induction was observed.

  容易制备的 2-烷基-2-叠氮丙基环烷基-1,3-二酮与一系列硬路易斯酸发生分子内施密特重排反应，生成吲哚二酮和吡咯氮杂环二酮。手性铝基路易斯酸也可用于介导这种打破对称性的转化，但没有观察到明显的不对称诱导。
• Overcoming Product Inhibition in Catalysis of the Intramolecular Schmidt Reaction
  作者：Hashim F. Motiwala、Charlie Fehl、Sze-Wan Li、Erin Hirt、Patrick Porubsky、Jeffrey Aubé

  DOI：10.1021/ja402848c

  日期：2013.6.19

  carrying out the intramolecular Schmidt reaction of alkyl azides and ketones using a substoichiometric amount of catalyst is reported. Following extensive screening, the use of the strong hydrogen-bond-donating solvent hexafluoro-2-propanol was found to be consistent with low catalyst loadings, which ranged from 2.5 mol % for favorable substrates to 25 mol % for more difficult cases. Reaction optimization

  报道了使用亚化学计量量的催化剂进行烷基叠氮化物和酮的分子内施密特反应的方法。经过广泛筛选，发现使用强氢键供体溶剂六氟-2-丙醇与低催化剂负载量一致，其范围从有利底物的 2.5 mol% 到更困难情况的 25 mol%。描述了反应优化、广泛的底物范围和这种改进版反应的初步机理研究。
• Chiral Brønsted Acid-Promoted Enantioselective Desymmetrization in an Intramolecular Schmidt Reaction of Symmetric Azido 1,3-Hexanediones: Asymmetric Synthesis of Azaquaternary Pyrroloazepine Skeletons
  作者：Ming Yang、Yu-Ming Zhao、Shu-Yu Zhang、Yong-Qiang Tu、Fu-Min Zhang

  DOI：10.1002/asia.201100171

  日期：2011.6.6

  The enantioselective desymmetrization of 2‐substituted‐2‐azidopropyl 1,3‐hexanediones through an asymmetric intramolecular Schmidt reaction using a chiral Brønsted acid has been developed for the first time. Synthetically interesting pyrroloazepine skeletons with an azaquaternary stereogenic center with up to 59 % ee are accessed effectively (see scheme; R=H, alkyl, or aryl).

  首次开发了使用手性布朗斯台德酸通过不对称分子内Schmidt反应对2-取代2-叠氮丙基1,3-己二酮进行对映选择性脱对称。合成有趣的吡咯并ze庚因骨架，其氮杂季铵立体异构中心的ee高达59％（请参阅方案； R = H，烷基或芳基）。
• Asymmetric Aza-Wittig Reactions: Enantioselective Synthesis of β-Quaternary Azacycles
  作者：Duanpen Lertpibulpanya、Stephen P. Marsden、Ignacio Rodriguez-Garcia、Colin A. Kilner

  DOI：10.1002/anie.200601383

  日期：2006.7.24
• Synthesis and Application of <i>P</i>-Stereogenic Phosphines as Superior Reagents in the Asymmetric Aza-Wittig Reaction
  作者：Catherine E. Headley、Stephen P. Marsden

  DOI：10.1021/jo0709908

  日期：2007.9.1

  [GRAPHICS]A wide variety of P-stereogenic aryldialkylphosphines were prepared in enantioenriched form by a systematic diversification of the (-)-sparteine-mediated dynamic kinetic resolution of racemic lithiophosphine-boranes reported by Livinghouse. Excellent asymmetric induction was observed provided that the intermediate lithiophosphine/sparteine complex precipitated from solution; more soluble derivatives returned poor ee's or racemic material. The resulting phosphine-boranes were deprotected and used as reagents in the desymmetrizing asymmetric aza-Wittig reaction of 2-alkyl-2-(3-azidopropyl)cyclohexane-1,3-diones, delivering the highest ee's yet observed in this process (up to 84% ee). Phosphines bearing bulky substituents required heating for the aza-Wittig reaction to proceed to completion, which P-31 NMR studies showed to be due to interception of the reaction by the formation of unreactive (E)-phosphazides. This was circumvented by use of methyltrioxorhenium to catalyze the formation of iminophosphoranes from the azide and phosphine, allowing reactions to take place at ambient temperature, although the ee's of the asymmetric reactions were reduced in these examples.