2,4-dimethyl-5-ketohexanoic acid | 2323-28-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2,4-dimethyl-5-ketohexanoic acid
• 英文别名: 2,4-dimethyl-5-oxohexanoic acid；5-Oxo-2,4-dimethyl-capronsaeure；Dimethyl-2,4-oxo-5-hexansaeure
• CAS: 2323-28-6
• 化学式: C₈H₁₄O₃
• 分子量: 158.197
• InChiKey: SPSSBFRNUFPFJQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,4-dimethyl-5-ketohexanoic acid 在 盐酸 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 24.0h， 生成 4,6-dimethyl-1,3-cyclohexanedione
  参考文献：
  名称：

  Mukherjee, Sukumar; Nasipuri, Dhanonjoy, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1984, vol. 23, # 3, p. 193 - 198

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,4S)-5-acetoxy-2,4-dimethyl-pentanal 在 sodium chlorite 、 disodium hydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 二甲基亚砜 作用下， 以 乙醚 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 7.0h， 生成 2,4-dimethyl-5-ketohexanoic acid
  参考文献：
  名称：

  鉴定工程化聚酮化合物生物合成中的关键瓶颈。

  摘要：

  组合生物合成的概念有望访问基于特权天然支架的化合物文库。自从1990年阐明向抗生素红霉素A的生物合成途径以来，一直在研究可预测的I型聚酮化合物合酶大酶的操作。但是，除了简化的模型系统之外，很少达到此目标。在这项研究中，我们使用靶向代谢组学方法鉴定了聚醚莫能菌素和许多突变变体的生物合成中间体。我们调查了中间体的生物合成流，并使用实验装置揭示了聚酮化合物合酶中选择性过滤器的存在。这些阻碍了酶促组装线中非天然中间体的加工。因此，我们质疑聚酮化合物合酶的真正模块化组织的概念，并强调了沿级联通道的底物通道中的障碍。在寻找选择性过滤器的分子起源时，我们研究了莫能菌素基因簇中不同硫酯酶的作用以及酮合成酶序列基序与传入底物结构之间的联系。此外，我们证明了选择性过滤器不适用于新生的聚酮化合物中的新到自然的侧链，这表明对它们的接受通常不受下游模块的限制。我们研究了莫能菌素基因簇中不同硫酯酶的作用以及酮合酶序列

  DOI：

  10.1039/c9ob00831d

文献信息

• METHOD FOR PRODUCING CARBOXYLIC ACID
  申请人：National Institute of Advanced Industrial Science and Technology

  公开号：EP1544190A1

  公开（公告）日：2005-06-22

  The present invention provides a safe, convenient and efficient method for producing carboxylic acid by a reaction of alicyclic alcohol with an aqueous hydrogen peroxide to thereby obtain carboxylic acid in high yield from alicyclic alcohol or alicyclic ketone under mild reaction conditions, wherein the reaction operation is simple and easy, a step for removing solvent after completion of the reaction is not necessary and influence and toxicity upon the environment and human body are markedly small. In order to provide it, an oily alicyclic alcohol is allowed to react with an aqueous hydrogen peroxide in the presence of a catalyst containing a metal compound belonging to Group 6 of the Periodic Table in a heterogeneous solution system.

  本发明提供了一种安全、方便、高效的生产羧酸的方法，该方法通过脂环醇与过氧化氢水溶液反应，从而在温和的反应条件下，从脂环醇或脂环酮中高产率地获得羧酸，反应操作简单易行，反应完成后无需去除溶剂的步骤，对环境和人体的影响和毒性明显较小。为了实现这一目标，需要在一个异相溶液体系中，在含有元素周期表第 6 族金属化合物的催化剂存在下，使油性脂环醇与过氧化氢水溶液发生反应。
• Method for producing carboxylic acid
  申请人：Sato Kazuhiko

  公开号：US20050215817A1

  公开（公告）日：2005-09-29

  The present invention provides a safe, convenient and efficient method for producing carboxylic acid by a reaction of alicyclic alcohol with an aqueous hydrogen peroxide to thereby obtain carboxylic acid in high yield from alicyclic alcohol or alicyclic ketone under mild reaction conditions, wherein the reaction operation is simple and easy, a step for removing solvent after completion of the reaction is not necessary and influence and toxicity upon the environment and human body are markedly small. In order to provide it, an oily alicyclic alcohol is allowed to react with an aqueous hydrogen peroxide in the presence of a catalyst containing a metal compound belonging to Group 6 of the Periodic Table in a heterogeneous solution system.

  本发明提供了一种安全、方便、高效的生产羧酸的方法，该方法通过脂环醇与过氧化氢水溶液反应，从而在温和的反应条件下，从脂环醇或脂环酮中高产率地获得羧酸，反应操作简单易行，反应完成后无需去除溶剂的步骤，对环境和人体的影响和毒性明显较小。为了实现这一目标，需要在一个异相溶液体系中，在含有元素周期表第 6 族金属化合物的催化剂存在下，使油性脂环醇与过氧化氢水溶液发生反应。
• Trolliet,M. et al., Bulletin de la Societe Chimique de France, 1974, p. 1484 - 1486
  作者：Trolliet,M. et al.

  DOI：——

  日期：——
• Carbon-13 NMR spectra of saturated heterocycles: XI—Tetrahydropyrans (oxanes)
  作者：Ernest L. Eliel、Muthiah Manoharan、K. Michal Pietrusiewicz、Karl D. Hargrave

  DOI：10.1002/omr.1270210205

  日期：1983.2

  AbstractThe 13C NMR spectra of 62 oxanes (tetrahydropyrans) with and without methyl substituents at various ring positions, some of them bearing in addition (or instead) ethyl, vinyl, ethynyl, carbomethoxy and methylol substituents at C‐2, have been recorded, and the 294 resulting chemical shifts have been correlated by multiple linear regression analysis. Axial and equatorial α‐, β‐, γ‐, δ‐, gem‐ and vic‐parameters for shifts caused by methyl groups at all ring positions, and similar parameters for Et,—CHCH2,—CCH, CO2Me and CH2OH groups at C‐2, are reported. Standard deviations of the parameters are, in most cases, within 0.3 ppm and the agreement of calculated and experimental shifts is excellent. This is probably the largest parameter set of this type extant. 13C NMR spectra of a number of additional substituted tetrahydropyrans, and of 3,6‐dihydro‐2H‐pyrans and 3,4‐dihydro‐2H‐pyrans, are tabulated and discussed.
• Mechanism and Stereospecificity of a Fully Saturating Polyketide Synthase Module: Nanchangmycin Synthase Module 2 and Its Dehydratase Domain
  作者：Xun Guo、Tiangang Liu、Chiara R. Valenzano、Zixin Deng、David E. Cane

  DOI：10.1021/ja1073432

  日期：2010.10.27

  Recombinant nanchangmycin synthase module 2 (NANS module 2), with the thioesterase domain from the 6-deoxyerythronolide B synthase (DEBS TE) appended to the C-terminus, was cloned and expressed in Escherichia coli. Incubation of NANS module 2+TE with (+/-)-2-methyl-3-keto-butyryl-N-acetylcysteamine thioester (1), the SNAC analog of the natural ACP-bound substrate, with methylmalonyl-CoA (MM-CoA) in the absence of NADPH gave 3,5,6-trimethy1-4-hydroxypyrone (2), identified by direct comparison with synthetic 2 by radio-TLC-phosphorimaging and LC-ESI(+)-MS-MS. The reaction showed K(cat) 0.5 +/- 0.1 min(-1) and K(m)(1) 19 +/- 5 mM at 0.5 mM MM-CoA and k(cat)(app) 0.26 +/- 0.02 min(-1) and K(m)(MM-CoA) 0.11 +/- 0.02 mM at 8 mM 1. Incubation in the presence of NADPH generated the fully saturated triketide chain elongation product as a 5:3 mixture of (2S,4R)-2,4-dimethy1-5-ketohexanoic acid (3a) and the diastereomeric (2S, 4S)-3b. The structure and stereochemistry of each product was established by comparison with synthetic 3a and 3b by a combination of radio-TLC-phosphorimaging and LC-ESI(-)-MS-MS, as well as chiral capillary GC-MS analysis of the corresponding methyl esters 3a-Me and 3b-Me. The recombinant dehydratase domain from NANS module 2, NANS DH2, was shown to catalyze the formation of an (E)-double bond by syndehydration of the ACP-bound substrate anti-(2R,3R,4S,5R)-2,4-dimethyl-3,5-dihydroxyheptanoyl-ACP6 (4), generated in situ by incubation of (2S,3R)-2-methyl-3-hydroxypentanoyl-SNAC (5), methylmalonyl-CoA, and NADPH with the recombinant [KS6][AT6] didomain and ACP6 from DEBS module 6 along with the ketoreductase from the tylactone synthase module 1 (TYLS KR1). These results also indirectly establish the stereochemistry of the reactions catalyzed by the KR and enoylreductase (ER) domains of NANS module 2.