(4R,5R)-5-羟基-4-甲基庚烷-3-酮 | 108864-90-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (4R,5R)-5-羟基-4-甲基庚烷-3-酮
• 英文名称: (4R,5R)-5-hydroxy-4-methyl-3-heptanone
• 英文别名: (4R,5R) sitophilure；(4R,5R)-5-hydroxy-4-methylheptan-3-one
• CAS: 108864-90-0
• 化学式: C₈H₁₆O₂
• 分子量: 144.214
• InChiKey: GEZUGFBWAPDBGZ-RNFRBKRXSA-N

物化性质

• 沸点：
  219.5±13.0 °C(Predicted)
• 密度：
  0.924±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (S)-(+)-alpha-甲氧基苯乙酸 、 (4R,5R)-5-羟基-4-甲基庚烷-3-酮 在 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 生成 (S)-Methoxy-phenyl-acetic acid (1R,2R)-1-ethyl-2-methyl-3-oxo-pentyl ester
  参考文献：
  名称：

  分离的酮还原酶合成有价值的手性中间体：在合成α-烷基-β-羟基酮和1,3-二元醇中的应用

  摘要：

  描述了通过使用可商购的酮还原酶（KRED）将α-取代的1，3-二酮区域和立体选择性还原为相应的β-酮醇或1，3-二醇。在一个或两个酶促还原步骤中，许多α-单烷基或二烷基取代的对称及非对称二酮的高光学纯度和化学收率得到降低。在大多数情况下，通过使用不同的酶来合成四种可能的α-烷基-β-酮醇非对映异构体中的两个甚至三个，并且在两个实例中，两种酮均还原为1,3-二醇。通过用OAc基团取代α-烷基取代基，可以以高光学纯度合成1-酮-2,3-二醇以及1,2,3-三醇。这些酶促反应提供了一种简单，

  DOI：

  10.1002/adsc.200606185
• 作为产物：
  描述：

  3-trimethylsiloxypenta-1,3-diene 在 bis(cyclopentadienyl)titanium (III) chloride 三氯硅烷 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 55.75h， 生成 (4R,5R)-5-羟基-4-甲基庚烷-3-酮
  参考文献：
  名称：

  A Versatile Approach Towards Enantiopure α-Methyl β-Hydroxy Ketones. Application to the Synthesis of (4R,5S) Sitophilure and of Its Stereoisomers

  摘要：

  Rice weevil pheromone sitophilure ((4R,5S)-5-hydroxy-4-methyl-3-heptanone) and its three diastereomers were synthesized in three steps, starting from 3-(trimethylsilyloxy)-1,3-pentadiene and propionaldehyde. Other optically active alpha-methyl beta-hydroxy ketones can also be synthesized by the reported procedure.

  DOI：

  10.1080/00397919808004830

文献信息

• Use of biological systems for the preparation of chiral molecules IV: A two-step chemoenzymatic synthesis of a natural pheromone (4R,5S)-(−)-4-methyl 5-hydroxy heptan 3-one, sitophilure.
  作者：Annie Fauve、Henri Veschambre

  DOI：10.1016/s0040-4039(00)96689-9

  日期：1987.1

  Reduction of 4-methyl heptan 3,5-dione by resting cells of provides natural sitophilure (4R,5S)-(−)-4-methyl 5-hydroxy heptan 3-one under anaerobic conditions. Diastereoisomer (4S,5S)-(+)-4-methyl 5-hydroxy heptan 3-one is obtained under aerobic conditions. Starting β-diketone is easily obtained by a one-pot synthesis. Good yield and high enantiomeric excess are obtained for the natural pheromone.

  通过静息细胞的4-甲基庚烷3,5-二酮还原，可在厌氧条件下提供天然的亲脂性（4R，5S）-（-）-4-甲基5-羟基庚烷3-一。在有氧条件下获得非对映异构体（4S，5S）-（+）-4-甲基5-羟基庚烷3-one 。通过一锅法合成很容易获得起始β-二酮。天然信息素获得了良好的收率和高的对映体过量。
• Synthesis of all of the four possible stereoisomers of 5-hydroxy-4-methyl-3-heptanone (sitophilure), the aggregation pheromone of the rice weevil and the maize weevil
  作者：Kenji Mori、Takashi Ebata

  DOI：10.1016/s0040-4020(01)87281-1

  日期：1986.1

  All of the four possible stereoisomers [(4,5)-, (4,5)-, (4,5)- and (4,5)-isomers] of 5-hydroxy-4-methyl-3-heptanone (sitophilure) were synthesized from methyl ()-3-hydroxypentanoate of microbial origin.

  所有的四种可能的立体异构体[（4- ，5 ）- ，（4 ，5 ）- ，（4 ，5 ）-和（4 ，5 ） -异构体] -5-羟基-4-甲基-3-庚酮（sitophilure ）是由微生物来源的（）-3-羟基戊酸甲酯合成的。
• Vegetables as biocatalysts in stereoselective hydrolysis of labile organic compounds
  作者：Björn Bohman、L. R. Cavonius、C. Rikard Unelius

  DOI：10.1039/b913936b

  日期：——

  Hydrolysis of labile esters of β-hydroxyketones has been performed with whole plant tissue from various vegetables. The pheromone 5-hydroxy-4-methyl-3-heptanone (1) was used as the model compound. Hydrolysis of acetates and benzoates of 1 was unsuccessful using normal conditions of ester hydrolysis, both by chemical hydrolysis and by the means of commercial lipases. When, however, whole cells of carrot, celery root, eggplant, parsley root, parsnip and potato were used as reagents, hydrolysis of the acetates was successful. At low conversion the hydrolysis was stereoselective and at total conversion virtually no formation of by-products was observed. The selectivity varied among the eight vegetables that were evaluated. Methods of preparation and substrate-to-plant ratio were examined. Furthermore, acetates and benzoates of three analogous compounds [5-hydroxy-3-heptanone (2), 5-hydroxy-5-methyl-3-heptanone (3) and 5-ethyl-6-hydroxy-4-octanone (4)] were hydrolyzed by potato and sweet potato to various degrees, indicating that the method is general for the mild and stereoselective hydrolysis of secondary β-alkoxy- and β-aryloxyketones.

  β-羟基酮的不稳定酯的水解已用各种蔬菜的整个植物组织进行。信息素 5-羟基-4-甲基-3-庚酮 (1) 用作模型化合物。使用正常的酯水解条件，无论是通过化学水解还是通过商业脂肪酶，1的乙酸酯和苯甲酸酯的水解均不成功。然而，当使用胡萝卜、芹菜根、茄子、欧芹根、防风草和马铃薯的全细胞作为试剂时，乙酸盐的水解是成功的。在低转化率下，水解是立体选择性的，并且在完全转化率下，几乎没有观察到副产物的形成。所评估的八种蔬菜的选择性各不相同。检查了制备方法和基质与植物的比例。此外，三种类似化合物的乙酸酯和苯甲酸酯[5-羟基-3-庚酮(2)、5-羟基-5-甲基-3-庚酮(3)和5-乙基-6-羟基-4-辛酮(4) ]被马铃薯和甘薯不同程度地水解，表明该方法对于仲β-烷氧基酮和β-芳氧基酮的温和立体选择性水解具有通用性。
• A highly enantioselective, moderately anti-selective aldol reaction using a novel hydrazone moiety as stereo director
  作者：Gerard P. McGlacken、Simon W. Breeden

  DOI：10.1016/j.tetasy.2005.09.027

  日期：2005.11

  with a view to develop a highly enantioselective, anti-diastereoselective aldol addition procedure has been investigated. A number of proline-derived hydrazones were produced and their effectiveness in directing simple alkylation of aza-enolates investigated. The most promising of these hydrazones were then used in the aldol reaction. The substituent on the oxygen of the proline had a profound effect

  为了开发高度对映选择性，反非对映选择性的醛醇加成方法，已经研究了使用新型作为立体导向剂。产生了许多脯氨酸衍生的azo，并研究了它们在指导简单的氮杂-烯醇酸酯烷基化反应中的有效性。然后将这些promising中最有希望的用于醛醇缩合反应。脯氨酸的氧上的取代基对幅度和不对称感应感都具有深远的影响。戊酮与丙醛之间进行正式羟醛反应的最佳给出了37％的非对映选择性，有利于抗异构体，而两种异构体的ee均为83-84％。
• Titanium(IV) Alkoxide Ligand Exchange with α-Hydroxy Acids:  The Enantioselective Aldol Addition
  作者：Rainer Mahrwald

  DOI：10.1021/ol0002727

  日期：2000.12.1

  Ligand exchange of titanium(IV) alkoxides with alpha-hydroxy acids presents an unexpected and novel approach to enantioselective aldol additions of aldehydes and ketones. The aldol products were isolated in a high degree of syn-diastereoselectivity. High enantioselectivities were observed by using simple optically pure alpha-hydroxy acids in this novel aldol addition.

  钛（IV）醇盐与α-羟基酸的配体交换为醛和酮的对映选择性羟醛加成提供了一种出乎意料的新颖方法。以高度的对非对映体选择性分离出羟醛产物。通过在这种新颖的醛醇缩合中使用简单的光学纯的α-羟基酸，观察到高对映选择性。