(4S,5S)-(+)-4-methyl 5-hydroxy heptan 3-one | 100483-73-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S,5S)-(+)-4-methyl 5-hydroxy heptan 3-one
• 英文别名: (4S,5S)-4-methyl-5-hydroxyheptan-3-one；(4S,5S)-5-hydroxy-4-methyl-3-heptanone；(4S)-5-hydroxy-4-methyl-heptan-3-one；(5S)-hydroxy-(4S)-methylheptan-3-one；anti-5-hydroxy-4-methyl-3-heptanone；(4S,5S) sitophilure；(4S,5S)-5-hydroxy-4-methylheptan-3-one
• CAS: 100483-73-6
• 化学式: C₈H₁₆O₂
• 分子量: 144.214
• InChiKey: GEZUGFBWAPDBGZ-BQBZGAKWSA-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：

  (4S,5S)-(+)-4-methyl 5-hydroxy heptan 3-one 在 glucose dehydrogenase 、 葡萄糖 、 ketoreductase 111 、 还原型辅酶II(NADPH)四钠盐 作用下， 反应 24.0h， 以75%的产率得到(3S,5S)-4-methyl-3,5-heptanediol
  参考文献：
  名称：

  Highly diastereoselective synthesis of 2-substituted-1,3-diols catalyzed by ketoreductases

  摘要：

  The stereoselective reduction of alpha-substituted-beta-hydroxy ketones for the preparation of the corresponding optically pure 2-monosubstituted or 2-disubstituted-1,3-diols is described. These transformations proceed in high optical purities and yields. Ketoreductases were able to catalyze the formation of either the syn or the anti diol, depending on the enzyme. By replacing the a-alkyl substituent for an OAc moiety, in low conversion time (<= 24 h), ketoreductases catalyzed the formation of the OAc-protected 1,2,3-triol, in high yield and with high optical purity (>99% de, >99% ee). This is a simple and highly stereoselective method for the synthesis of different diastereomers of chiral diols. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.09.096
• 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 (4S,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

• Synthesis of (+)-Discodermolide by Catalytic Stereoselective Borylation Reactions
  作者：Zhiyong Yu、Robert J. Ely、James P. Morken

  DOI：10.1002/anie.201405455

  日期：2014.9.1

  1990 and, to this day, remains a compelling synthesis target. Not only does the compound possess fascinating biological activity, but it also presents an opportunity to test current methods for chemical synthesis and provides an inspiration for new reaction development. A new synthesis of discodermolide employs a previously undisclosed stereoselective catalytic diene hydroboration and also establishes

  海洋天然产物 (+)-discodermolide 于 1990 年首次分离出来，至今仍是一个引人注目的合成目标。该化合物不仅具有令人着迷的生物活性，而且还为测试现有化学合成方法提供了机会，并为新反应的开发提供了灵感。 discodermolide 的新合成采用了先前未公开的立体选择性催化二烯硼氢化反应，并且还建立了手性烯醇化物烷基化的策略。此外，discodermolide 的这种合成提供了复杂分子合成中二烯不对称 1,4-二硼化和硼基化二烯-醛偶联的第一个例子。
• 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。
• Chemoenzymatic Dynamic Kinetic Asymmetric Transformations of β‐Hydroxyketones
  作者：Simon Hilker、Daniels Posevins、C. Rikard Unelius、Jan‐E. Bäckvall

  DOI：10.1002/chem.202102683

  日期：2021.11.11

  one-pot procedure to achieve efficient DYKAT of α-substituted β-hydroxyketones. This newly developed protocol offers straightforward access to enantiomerically pure and diastereomerically enriched β-oxoacetates in high yields by employing a ruthenium-based racemization catalyst for efficient racemization-epimerization of substrates via formation of non-chiral 1,3-diketone intermediates.

  将钌和酶催化结合在一锅法中，实现 α-取代 β-羟基酮的高效 DYKAT。这种新开发的方案通过采用钌基外消旋催化剂，通过形成非手性 1,3-二酮中间体，实现底物的高效外消旋差向异构化，从而以高产率直接获得对映体纯和非对映体富集的 β-氧代乙酸酯。
• 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。