壬烷-2,6-二酮 | 36452-81-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 壬烷-2,6-二酮
• 英文名称: 2,6-nonanedione
• 英文别名: Nonan-dion-2.6；Nonane-2,6-dione
• CAS: 36452-81-0
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: CSXNKDHJFCFQOY-UHFFFAOYSA-N

物化性质

• 熔点：
  36-37 °C
• 沸点：
  84-85 °C(Press: 2 Torr)
• 密度：
  0.911±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  壬烷-2,6-二酮 生成 2-ethyl-3-methylcyclohex-2-en-1-one
  参考文献：
  名称：

  Ferard-Brunner,J. et al., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1972, vol. 274, p. 2111 - 2114

  摘要：

  DOI：
• 作为产物：
  描述：

  5-氯-2-戊酮 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 壬烷-2,6-二酮
  参考文献：
  名称：

  Masked lithium bishomoenolates: useful intermediates in organic synthesis

  摘要：

  The lithiation of the chloro ketals 9 with lithium naphthalenide at -78-degrees-C led to the corresponding masked lithium bishomoenolates 4, which are stable species under these conditions and react with different electrophilic reagents (H2O, D2O, i-PrCHO, PhCHO, MeCOEt, (activated CH2)4CO, (activated CH2)5CO, (activated CH2)7CO, PhCOMe, c-C3H5COPh, PhCN, HCONMe2, PrCO activated N(CH2)4, PhCO activated N(CH2)4, PhCOCl, EtOCOCl, PhCHNPh, and (PhCH2S)2) to give, after hydrolysis with water, the corresponding bifunctionalized compounds 10a-22a, 10b-22b, and 10c-15c. When alkyl halides were used as electrophiles the reaction failed. In the presence of a catalytic amount of the complex CuBr.Me2S, the same reaction with alpha,beta-unsaturated ketones (methyl vinyl ketone or 2-cyclohexanone) yielded the expected products of a 1,4-addition 25a-c and 26b. The deprotection of the masked carbonyl group was easily done by treatment with 2 N hydrochloric acid in THF, so as examples, compounds 27a-29a, 30b, 31b, 32c, and 33c were isolated. The transformation of hemiacetals of the type 27a into substituted tetrahydropyrans was carried out by means of compounds of the type R3SiNu (Nu = H, allyl, CN) in the presence of BF3, so products 34a-41a, 42b, and 43b were prepared. Finally, the in situ oxidation of the deprotected products of the type 27a-arising from the reaction of bishomoenolate 4a with carbonyl compounds-with Jones reagent (for ketones derivatives) or PCC (for aldehydes derivatives) led to the corresponding delta-lactones 44-57.

  DOI：

  10.1021/jo00012a012

文献信息

• New ketone homoenolate anion equivalents derived from (alkenyl)pentamethyl phosphoric triamides
  作者：Claude Grison、Antoine Thomas、Frédéric Coutrot、Philippe Coutrot

  DOI：10.1016/s0040-4020(03)00188-1

  日期：2003.3

  Lithiated ambident anions derived from (1-alkyl-2-propenyl)- or (1-phenyl-2-propenyl)-pentamethyl phosphoric triamides undergo regioselectively γ-reaction with various alkylating reagents and isobutyraldehyde. Further hydrolysis of adducts releases the ketone under acid conditions. Number of synthetic applications clearly show the ketone homoenolate behaviour of these new carbanions.

  衍生自（1-烷基-2-丙烯基）-或（1-苯基-2-丙烯基）-五甲基磷酸三酰胺的锂化环境阴离子与各种烷基化试剂和异丁醛进行区域选择性的γ反应。加合物的进一步水解在酸性条件下释放出酮。合成应用的数量清楚地表明了这些新碳负离子的酮均烯酸酯行为。
• Regio- and Stereoselective Monoamination of Diketones without Protecting Groups
  作者：Robert C. Simon、Barbara Grischek、Ferdinand Zepeck、Andreas Steinreiber、Ferdinand Belaj、Wolfgang Kroutil

  DOI：10.1002/anie.201202375

  日期：2012.7.2

  Hitting the right target: Differentiation between two keto moieties was accomplished by a regio‐ and enantioselective bioamination employing ω‐transaminases. Using 1,5‐diketones as substrates gave access to the optically pure 2,6‐disubstituted piperidine scaffold. The approach allowed the shortest synthesis of the alkaloid dihydropinidine, as well as its enantiomer, by choosing an appropriate ω‐transaminase

  达到正确的目标：通过使用ω-转氨酶进行区域和对映选择性生物胺化，可实现两个酮基部分的区分。使用1,5-二酮作为底物可以进入光学纯的2,6-二取代的哌啶骨架。通过选择合适的ω-转氨酶，该方法可以最短地合成生物碱二氢吡啶及其对映体。
• One-Pot Cascade Synthesis of Mono- and Disubstituted Piperidines and Pyrrolidines using Carboxylic Acid Reductase (CAR), ω-Transaminase (ω-TA), and Imine Reductase (IRED) Biocatalysts
  作者：Scott P. France、Shahed Hussain、Andrew M. Hill、Lorna J. Hepworth、Roger M. Howard、Keith R. Mulholland、Sabine L. Flitsch、Nicholas J. Turner

  DOI：10.1021/acscatal.6b00855

  日期：2016.6.3

  Access to enantiomerically pure chiral mono- and disubstituted piperidines and pyrrolidines has been achieved using a biocatalytic cascade involving carboxylic acid reductase (CAR), ω-transaminase (ω-TA), and imine reductase (IRED) enzymes. Starting from keto acids or keto aldehydes, substituted piperidine or pyrrolidine frameworks can be generated in high conversion, ee, and de in one pot, with each

  使用涉及羧酸还原酶（CAR），ω-转氨酶（ω-TA）和亚胺还原酶（IRED）的生物催化级联反应，可获得对映体纯的手性单和双取代哌啶和吡咯烷。从酮酸或酮醛开始，可以在一锅中以高转化率，ee和de生成高取代度的哌啶或吡咯烷骨架，每种生物催化剂在催化过程中均表现出化学，区域和/或立体选择性。该研究还包括对甲基环取代基位置对IRED催化手性亚胺还原的影响的系统研究。在这些反应中观察到的选择性分析表明，底物与酶控制之间存在有趣的平衡。
• Asymmetric Synthesis of Dihydropinidine Enabled by Concurrent Multienzyme Catalysis and a Biocatalytic Alternative to Krapcho Dealkoxycarbonylation
  作者：Natália Alvarenga、Stefan E. Payer、Philipp Petermeier、Christoph Kohlfuerst、André Luiz Meleiro Porto、Joerg H. Schrittwieser、Wolfgang Kroutil

  DOI：10.1021/acscatal.9b04611

  日期：2020.1.17

  nonane-2,6-dione. This diketone is then converted into dihydropinidine by a concurrent one-pot (cascade) biotransformation catalyzed by a transaminase, an imine reductase, and an alcohol dehydrogenase. High yields and excellent regio- and stereoselectivities of the individual transformations render chromatographic purification of intermediates unnecessary and make it possible to carry out the entire sequence

  二氢吡啶是一种在云杉针叶中发现的哌啶生物碱，对大松象鼻是一种有希望的拒食活性，大松象鼻是一种针叶树人工林的广泛且与经济相关的害虫。先前已显示化学酶法可以经济地逐步获得该生物碱的两种对映体，但这些合成方法的可扩展性受到限制。在本文中，我们报告了以化学催化途径主导的二氢吡啶的化学酶促路线，该路线以生物催化步骤为主，并以优良的立体异构纯度（> 99％ee和de）和高收率（总体为57％）提供目标生物碱（以克计）。我们的合成方法采用无溶剂，路易斯酸催化的迈克尔加成反应，以及通过猪肝酯酶（PLE）催化的酯水解和酸化作用实现的Krapcho脱氧羰基化的生物催化替代物，专门为此目的而开发的，用于访问关键中间体壬烷2,6-二酮。然后通过转氨酶，亚胺还原酶和醇脱氢酶催化的同时一锅（级联）生物转化法将该二酮转化为二氢吡啶。单个转化的高收率和出色的区域选择性和立体选择性使中间体的色谱纯化成为不必要，并且有可能以目
• Chemoenzymatic Synthesis of All Four Diastereomers of 2,6-Disubstituted Piperidines through Stereoselective Monoamination of 1,5-Diketones
  作者：Robert C. Simon、Ferdinand Zepeck、Wolfgang Kroutil

  DOI：10.1002/chem.201202793

  日期：2013.2.18

  evaluated for the stereoselective monoamination of designated 1,5‐diketones; excellent conversions, enantio‐ and regioselectivities were observed. The resulting amino‐ketones underwent spontaneous intramolecular ring closure to afford Δ1‐piperideines, which served as precursors for the cis‐ and anti‐piperidine scaffold as demonstrated for the synthesis of the alkaloids dihydropinidine and epi‐dihydropinidine

  评估了各种对映体互补ω-转氨酶对指定的1,5-二酮的立体选择性单胺化的区域选择性；观察到优异的转化率，对映体和区域选择性。产生的氨基酮自发进行分子内闭环反应，得到Δ1-哌啶，它们作为顺式和反式哌啶骨架的前体，如生物碱二氢吡啶和表皮二氢吡啶的合成所证明。成功获得反式哌啶的关键是在还原步骤中路易斯酸介导的Δ1-哌啶的构象变化。因此，可以成功制备2,6-二取代哌啶的所有四个非对映异构体。