(2R,5S)-2-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohexanone | 288264-99-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (2R,5S)-2-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohexanone
• 英文别名: (1R,4S)-1-hydroxylimonen-2-one；(2R,5S)-2-hydroxy-2-methyl-5-prop-1-en-2-ylcyclohexan-1-one
• CAS: 288264-99-3
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: JEQLRDRDFLXSHY-WCBMZHEXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,5S)-2-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohexanone 在 2,6-二甲基吡啶 、 sodium hypochlorite 、 sodium tetrahydroborate 、 正丁基锂 、 偶氮二异丁腈 、 cerium(III) chloride heptahydrate 、 三(三甲基硅基)硅烷 、 四丁基氟化铵 、 双(三甲基硅烷基)氨基钾 、 sodium iodide 、 copper(ll) bromide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 丙酮 、 甲苯 、 叔丁醇 、 苯 为溶剂， 反应 8.5h， 生成 (1S,2S,3S,4R)-3-(2-((1S,3S,4R)-3-bromo-4-hydroxy-4-methylcyclohexyl)allyl)-1-methyl-4-(prop-1-en-2-yl)cyclohexane-1,2-diol
  参考文献：
  名称：

  Synthesis of the Proposed Structures of Prevezol C

  摘要：

  The first enantioselective synthesis of the proposed relative structures of Prevezol C is reported in 11 linear steps from readily available materials. The unusual syn bromohydrin was installed via a multistep sequence culminating in a diastereoselective geminal dibromide reduction. Discrepancies in the spectral data of the synthetic materials and the natural sample have led to the conclusion that the proposed structures are incorrect

  DOI：

  10.1021/ol400754e
• 作为产物：
  描述：

  (−)-氧化柠檬烯（顺反异构体混合物） 在 potassium phosphate 、 2-iodoxybenzoic acid 作用下， 以 aq. phosphate buffer 、 乙酸乙酯 为溶剂， 反应 48.0h， 生成 (2R,5S)-2-hydroxy-2-methyl-5-(prop-1-en-2-yl)cyclohexanone
  参考文献：
  名称：

  Synthesis of the Proposed Structures of Prevezol C

  摘要：

  The first enantioselective synthesis of the proposed relative structures of Prevezol C is reported in 11 linear steps from readily available materials. The unusual syn bromohydrin was installed via a multistep sequence culminating in a diastereoselective geminal dibromide reduction. Discrepancies in the spectral data of the synthetic materials and the natural sample have led to the conclusion that the proposed structures are incorrect

  DOI：

  10.1021/ol400754e

文献信息

• <i>Rhodococcus erythropolis</i> DCL14 Contains a Novel Degradation Pathway for Limonene
  作者：Mariët J. van der Werf、Henk J. Swarts、Jan A. M. de Bont

  DOI：10.1128/aem.65.5.2092-2102.1999

  日期：1999.5

  Strain DCL14, which is able to grow on limonene as a sole source of carbon and energy, was isolated from a freshwater sediment sample. This organism was identified as a strain of Rhodococcus erythropolis by chemotaxonomic and genetic studies. R. erythropolis DCL14 also assimilated the terpenes limonene-1,2-epoxide, limonene-1,2-diol, carveol, carvone, and (−)-menthol, while perillyl alcohol was not utilized as a carbon and energy source. Induction tests with cells grown on limonene revealed that the oxygen consumption rates with limonene-1,2-epoxide, limonene-1,2-diol, 1-hydroxy-2-oxolimonene, and carveol were high. Limonene-induced cells of R. erythropolis DCL14 contained the following four novel enzymatic activities involved in the limonene degradation pathway of this microorganism: a flavin adenine dinucleotide- and NADH-dependent limonene 1,2-monooxygenase activity, a cofactor-independent limonene-1,2-epoxide hydrolase activity, a dichlorophenolindophenol-dependent limonene-1,2-diol dehydrogenase activity, and an NADPH-dependent 1-hydroxy-2-oxolimonene 1,2-monooxygenase activity. Product accumulation studies showed that (1 S ,2 S ,4 R )-limonene-1,2-diol, (1 S ,4 R )-1-hydroxy-2-oxolimonene, and (3 R )-3-isopropenyl-6-oxoheptanoate were intermediates in the (4 R )-limonene degradation pathway. The opposite enantiomers [(1 R ,2 R ,4 S )-limonene-1,2-diol, (1 R ,4 S )-1-hydroxy-2-oxolimonene, and (3 S )-3-isopropenyl-6-oxoheptanoate] were found in the (4 S )-limonene degradation pathway, while accumulation of (1 R ,2 S ,4 S )-limonene-1,2-diol from (4 S )-limonene was also observed. These results show that R. erythropolis DCL14 metabolizes both enantiomers of limonene via a novel degradation pathway that starts with epoxidation at the 1,2 double bond forming limonene-1,2-epoxide. This epoxide is subsequently converted to limonene-1,2-diol, 1-hydroxy-2-oxolimonene, and 7-hydroxy-4-isopropenyl-7-methyl-2-oxo-oxepanone. This lactone spontaneously rearranges to form 3-isopropenyl-6-oxoheptanoate. In the presence of coenzyme A and ATP this acid is converted further, and this finding, together with the high levels of isocitrate lyase activity in extracts of limonene-grown cells, suggests that further degradation takes place via the β-oxidation pathway.

  摘要 从淡水沉积物样本中分离出了 DCL14 菌株，该菌株能够以柠檬烯作为唯一的碳和能量来源进行生长。经鉴定，该生物属于 Rhodococcus erythropolis 的菌株。 红球菌 DCL14 还吸收萜烯类化合物柠檬烯-1,2-环氧乙烷、柠檬烯-1,2-二醇、香芹酚、香芹酮和 (-)- 薄荷醇，而未将 perillyl 醇用作碳和能量来源。用柠檬烯诱导细胞的试验表明，柠檬烯-1,2-环氧化物、柠檬烯-1,2-二醇、1-羟基-2-氧代柠檬烯和香芹酮的耗氧率很高。柠檬烯诱导的 R. erythropolis DCL14 细胞含有以下四种参与该微生物柠檬烯降解途径的新型酶活性：依赖于黄素腺嘌呤二核苷酸和 NADH 的柠檬烯-1,2-单加氧酶活性、不依赖于辅助因子的柠檬烯-1,2-环氧化物水解酶活性、依赖于二氯苯酚靛酚的柠檬烯-1,2-二醇脱氢酶活性和依赖于 NADPH 的 1- 羟基-2-氧代柠檬烯-1,2-单加氧酶活性。产物积累研究表明，（1 S ,2 S ,4 R )-1,2-亚甲基二醇，(1 S ,4 R )-1-羟基-2-氧代柠檬烯和(3 R )-3-异丙烯基-6-氧代庚酸酯的中间体。 R )-柠檬烯降解途径的中间产物。相反的对映体[(1 R ,2 R ,4 S )-1,2-亚甲基二醇，(1 R ,4 S )-1-羟基-2-氧代柠檬烯和(3 S )-3-异丙烯基-6-氧代庚酸酯]中发现了(4S) S )-柠檬烯降解途径中，而(1-R) R ,2 S ,4 S )-1,2-亚甲基丙烯二醇从(4 S )-亚甲烯醇中提取的。这些结果表明 R. erythropolis DCL14 通过一种新的降解途径代谢柠檬烯的两种对映体，该途径首先在 1,2 双键处发生环氧化反应，形成柠檬烯-1,2-环氧化物。这种环氧化物随后会转化为柠檬烯-1,2-二醇、1-羟基-2-氧代柠檬烯和 7-羟基-4-异丙烯基-7-甲基-2-氧代氧杂环庚酮。这种内酯会自发地重新排列形成 3-异丙烯基-6-氧代庚酸酯。在辅酶 A 和 ATP 的存在下，这种酸会进一步转化，这一发现以及柠檬烯生长细胞提取物中高水平的异柠檬酸裂解酶活性表明，进一步降解是通过 β 氧化途径进行的。
• Purification and characterization of a Baeyer‒Villiger mono-oxygenase from Rhodococcus erythropolis DCL14 involved in three different monocyclic monoterpene degradation pathways
  作者：Mariët J. VAN DER WERF

  DOI：10.1042/0264-6021:3470693

  日期：2000.5.1

  A Baeyer-Villiger mono-oxygenase (BVMO), catalysing the NADPH- and oxygen-dependent oxidation of the monocyclic monoterpene ketones 1-hydroxy-2-oxolimonene, dihydrocarvone and menthone, was purified to homogeneity from Rhodococcus erythropolis DCL14. Monocyclic monoterpene ketone mono-oxygenase (MMKMO) is a monomeric enzyme of molecular mass 60 kDa. It contains 1 mol of FAD/monomer as the prosthetic

  从红红球菌DCL14中纯化Baeyer-Villiger单加氧酶（BVMO），以催化NADPH和氧依赖性氧化单环单萜酮1-羟基-2-氧杂环丁烯酮，二氢香芹酮和薄荷酮。单环单萜酮单加氧酶（MMKMO）是分子量为60 kDa的单体酶。它包含1摩尔FAD /单体作为修复基团。N末端氨基酸序列显示出与许多其他NADPH依赖性和含FAD（1型）BVMO同源。在pH 9和35摄氏度下测量了最大的酶活性。MMKMO具有广泛的底物特异性，可催化大量单环单萜酮和取代的环己酮的内酯化。天然底物1-羟基-2-氧杂环丁烯，将二氢香芹酮和薄荷酮化学计量地转化为3-异丙烯基-6-氧庚酸（MMKMO形成的内酯的自发重排产物），4-异丙烯基-7-甲基-2-氧代-氧杂戊酮和7-异丙基-4-甲基-2 -氧代-氧杂戊酮。MMKMO催化的异二氢香芹酮的转化显示出与二氢香芹酮相反的区域选择性。在这种情况下，形成6-异丙烯基-3-甲
• Synthesis of the Proposed Structures of Prevezol C
  作者：Anna E. Leung、Michael Blair、Craig M. Forsyth、Kellie L. Tuck

  DOI：10.1021/ol400754e

  日期：2013.5.3

  The first enantioselective synthesis of the proposed relative structures of Prevezol C is reported in 11 linear steps from readily available materials. The unusual syn bromohydrin was installed via a multistep sequence culminating in a diastereoselective geminal dibromide reduction. Discrepancies in the spectral data of the synthetic materials and the natural sample have led to the conclusion that the proposed structures are incorrect