(4R,5S)-(-)-4-methyl 5-hydroxy heptan 3-one | 108815-20-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4R,5S)-(-)-4-methyl 5-hydroxy heptan 3-one
• 英文别名: (4R,5S)-(-)-5-hydroxy-4-methyl-3-heptanone；(4R,5S)-5-hydroxy-4-methyl-3-heptanone；syn-5-hydroxy-4-methyl-3-heptanone；(4R,5S) sitophilure；sitophilure；(4R,5S)-5-hydroxy-4-methylheptan-3-one
• CAS: 108815-20-9
• 化学式: C₈H₁₆O₂
• 分子量: 144.214
• InChiKey: GEZUGFBWAPDBGZ-RQJHMYQMSA-N

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：

  (4R,5S)-(-)-4-methyl 5-hydroxy heptan 3-one 在 吡啶 、 四氯化钛 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 37.0h， 生成 (2RS,3SR)-2,6-diethyl-2,3-dihydro-3,5-dimethyl-4H-pyran-4-one
  参考文献：
  名称：

  β-酰氧基-酮的环缩合立体控制合成多取代的2,3-二氢-4 H-吡喃-4-酮

  摘要：

  当用TiCl 4 / EtN（i-Pr）2处理时，合成-β-酰氧基酮6和抗-β-酰氧基酮17会经历平滑的分子内烯醇酸酯/酯缩合6 18和17 19。因此，容易以立体选择性的方式制备三和四取代的顺式或反式-2,3-二氢-4 H-吡喃-4-酮。

  DOI：

  10.1002/hlca.19930760315
• 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 、 六甲基磷酰三胺 、 甲苯 为溶剂， 反应 55.75h， 生成 (4R,5S)-(-)-4-methyl 5-hydroxy heptan 3-one
  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

• A Flexible Stereocontrolled Synthesis of β-Hydroxy-α-methyl Esters: Application to the Synthesis of Stegobiol and Serricorole
  作者：Pilar Gil、Jesús Razkin、Alberto González

  DOI：10.1055/s-1998-2052

  日期：1998.4

  β-Hydroxy-α-methyl esters have been obtained in a stereocontrolled manner and high enantiomeric and diastereomeric purity from commercially available methyl 3-oxopentanoate and methyl 3-oxobutanoate. The key step is the catalytic hydrogenation of the carbonyl group using (R)- or (S)-BINAP-Ru as chiral catalyst followed by asymmetric alkylation. Stegobiol and serricorole, components of the sex pheromone of the drugstore beetle, Stegobium paniceum (L.) and cigarette beetle, Lasioderma serricorne (F.), have been prepared from these chiral building blocks without the need for stoichiometric amounts of chiral auxiliaries.

  利用市售的甲基3-氧代戊酸酯和甲基3-氧代丁酸酯，可以通过立体控制的方式合成具有高对映异构体纯度和非对映异构体纯度的β-羟基-α-甲酯。关键步骤是使用手性催化剂(R)-或(S)-BINAP-Ru对羰基进行催化氢化，随后进行不对称烷基化。药物甲虫（Stegobium paniceum L.）和烟甲虫（Lasioderma serricorne F.）的性信息素成分Stegobiol和Serricorole就是从这些手性构建模块中合成的，无需使用等量的手性辅助剂。
• Synthesis of Valuable Chiral Intermediates by Isolated Ketoreductases: Application in the Synthesis of α-Alkyl-β-hydroxy Ketones and 1,3-Diols
  作者：Dimitris Kalaitzakis、J. David Rozzell、Ioulia Smonou、Spiros Kambourakis

  DOI：10.1002/adsc.200606185

  日期：2006.9

  and in two examples both ketones were reduced to the 1,3-diol. By replacing the α-alkyl substituent with the OAc group, 1-keto-2,3-diols, as well as 1,2,3-triols were synthesized in high optical purities. These enzymatic reactions provide a simple, highly stereoselective and quantitative method for the synthesis of different diastereomers of valuable chiral synthons from non-chiral, easily accessible

  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，
• 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。
• Enantioselective acylation of enolates; the reaction of (4R)-trans-diethyl 2-alkyl-2-methoxy-1,3-dioxolane-4,5-dicarboxylates with E- and Z-silyl enol ethers
  作者：Tiziana Basile、Luigi Longobardo、Emilio Tagliavini、Claudio Trombini、Achille Umani-Ronchi

  DOI：10.1039/c39910000391

  日期：——

  The stereoselectivity of the Lewis acid induced acylation of open-chain silyl enoi ethers by chiral orthoesters is strongly affected by the CC bond configuration: both Z and E silyl enol ethers are acylated in good isolated yields, but the Z isomers give rise to a 1 : 1 ratio of diastereoisomeric monoprotected 1,3-diketones, while excellent stereoselectivities are obtained with E enols.

  路易斯酸诱导的开链硅醇醚与手性邻醇酸酯的酰化反应的立体选择性受到碳碳键构型的强烈影响：Z型和E型硅醇醚均可获得良好的单体收率，但Z型异构体产生1:1的立体异构单保护1,3-二酮的比例，而E型醇则获得出色的立体选择性。
• Asymmetric Aldol Reactions Using (<i>S</i>,<i>S</i>)-(<i>+</i>)-Pseudoephedrine-Based Amides:  Stereoselective Synthesis of α-Methyl-β-hydroxy Acids, Esters, Ketones, and 1,3-Syn and 1,3-Anti Diols
  作者：Jose L. Vicario、Dolores Badía、Esther Domínguez、Mónica Rodríguez、Luisa Carrillo

  DOI：10.1021/jo000035h

  日期：2000.6.1

  reactions is reported. The reaction of (S, S)-(+)-pseudoephedrine-derived propionamide enolates with several aldehydes yielded exclusively one of the four possible diastereomers in good yields, although transmetalation of the firstly generated lithium enolate with a zirconium(II) salt, prior to the addition of the aldehyde, is necessary in order to achieve high syn selectivity. The so-formed syn-alpha-methyl-beta-hydroxy

  报道了进行立体选择性醛醇缩合反应的非常有效的方法。（S，S）-（+）-伪麻黄碱衍生的丙酰胺烯醇化物与几种醛的反应仅以良好的收率仅产生了四种可能的非对映异构体之一，尽管先生成的烯醇酸锂与锆（​​II）盐进行了重金属化。为了获得高的顺式选择性，添加醛是必需的。如此形成的顺-α-甲基-β-羟基酰胺被转化为其他有价值的手性非外消旋合成子，例如α-甲基-β-羟基酸，酯和酮。最后，已经开发了一种立体控制的还原程序，该程序从如此获得的α-甲基-β-羟基酮开始，可以合成1,3-syn-或1,3-抗-α-甲基-1，