(2S,3R)-2-hydroxy-3-methyl-4-hexanone | 89794-67-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3R)-2-hydroxy-3-methyl-4-hexanone
• 英文别名: 5-hydroxy-4-methylhexan-3-one；(4R,5S)-5-hydroxy-4-methylhexan-3-one
• CAS: 89794-67-2；108167-08-4；108161-63-3
• 化学式: C₇H₁₄O₂
• 分子量: 130.187
• InChiKey: KEDWFAKTLVWTRU-RITPCOANSA-N

物化性质

• 沸点：
  89-90 °C(Press: 14 Torr)
• 密度：
  0.933±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  (2S,3R)-2-hydroxy-3-methyl-4-hexanone 在 glucose dehydrogenase 、 葡萄糖 、 ketoreductase 101 、 还原型辅酶II(NADPH)四钠盐 作用下， 以95%的产率得到(2S,3R,4S)-3-methyl-2,4-hexanediol
  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：

  (R)-2-(tert-Butyldimethylsilyl)pentan-3-on 在 tetrafluoroboric acid 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 (2S,3R)-2-hydroxy-3-methyl-4-hexanone
  参考文献：
  名称：

  Enders, Dieter; Lohray, Braj Bhushan, Angewandte Chemie, 1988, vol. 100, # 4, p. 594 - 596

  摘要：

  DOI：

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。
• Chemoenzymatic Synthesis of Stegobinone and Stegobiol, Components of the Natural Sex Pheromone of the Drugstore Beetle (Stegobium paniceum L.)
  作者：Dimitris Kalaitzakis、Ioulia Smonou

  DOI：10.1002/ejoc.201101319

  日期：2012.1

  NADPH-dependent ketoreductases were used for the chemoenzymatic stereoselective synthesis of the two componentsof the natural sex pheromone of the drugstore beetle. The key step in the asymmetric synthesis was the enzymatic reduction of an α-methyl-1,3-diketone and an α-methyl-β-keto ester, which finally led to the preparation of crystalline stegobinone and stegobiol.

  NADPH依赖性酮还原酶用于药店甲虫天然性信息素的两种成分的化学酶促立体选择性合成。不对称合成的关键步骤是酶促还原 α-甲基-1,3-二酮和 α-甲基-β-酮酯，最终制备出结晶 stegobinone 和 stegobiol。
• Iron- and Bismuth-Catalyzed Asymmetric Mukaiyama Aldol Reactions in Aqueous Media
  作者：Taku Kitanosono、Thierry Ollevier、Shū Kobayashi

  DOI：10.1002/asia.201301149

  日期：2013.12

  asymmetric Mukaiyama aldol reactions of silicon enolates with aldehydes catalyzed by chiral FeII and BiIII complexes. Although previous reactions often required relatively harsh conditions, such as strictly anhydrous conditions, very low temperatures (−78 °C), etc., the reactions reported herein proceeded in the presence of water at 0 °C. To find appropriate chiral water‐compatible Lewis acids for the

  我们已经开发了手性Fe II和Bi III配合物催化的烯醇硅与醛的不对称Mukaiyama aldol反应。尽管先前的反应通常需要相对苛刻的条件，例如严格的无水条件，非常低的温度（-78°C）等，但本文报道的反应是在0°C的水存在下进行的。为了找到适合手性与水相容的路易斯酸用于Mukaiyama醛醇缩合反应，我们筛选了许多路易斯酸与手性联吡啶L1结合，后者以前被发现是水性介质中合适的手性配体。三种类型的手性催化剂，由Fe II或Bi III金属盐，手性配体（L1），和添加剂已被发现和各种各样的基材（硅烯醇化物和醛）反应，通过三个催化体系中的一个的适当的选择，以得到所需的醛醇缩合产物以高收率和高diastereo-和对映选择性。机理研究阐明了Fe II和Bi III中心周围的配位环境以及添加剂对手性催化的影响。值得注意的是，布朗斯台德酸和碱在Fe II催化反应中都是有效的添加剂。假定的催化循
• 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，
• Catalytic asymmetric synthesis of α-methylene-β-hydroxy-ketones
  作者：Anthony G. M. Barrett、Akio Kamimura

  DOI：10.1039/c39950001755

  日期：——

  Condensation of an α,β-unsaturated ketone, an aldehyde and trimethylsilyl phenyl sulfide or selenide, catalysed by a chiral (acyioxy)borane, and subsequent oxidative elimination gives the title adducts in high enantiomeric excess.

  在手性（酰氧基）硼烷的催化下，δ,δ-不饱和酮、醛和三甲基硅苯基硫醚或硒化物发生缩合反应，随后发生氧化消除反应，生成对映体高度过剩的标题加合物。