(2S,3S)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one | 149561-65-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,3S)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one
• 英文别名: (2S,3S)-2-methyl-3-phenylmethoxy-2,3-dihydropyran-4-one
• CAS: 149561-65-9
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: RVCHBHBGYLNRKV-GWCFXTLKSA-N

物化性质

• 沸点：
  322.1±31.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3S)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one 在 sodium hydride 、 lithium tri-t-butoxyaluminum hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 生成 1,5-Anhydro-3,4-di-O-benzyl-2,6-didesoxy-L-ribo-hex-1-enit
  参考文献：
  名称：

  叔丁基亚硝酸盐存在下由钯和苯胺催化钯催化一锅立体定向合成2-脱氧芳基C-糖苷

  摘要：

  抽象的 在温和的条件下，在亚硝酸叔丁酯和HBF 4水溶液存在下，由糖和苯胺实现钯催化的一锅合成2,3-脱氧-3-酮芳基C-糖苷。这种一锅法在室温下以高收率立体地提供α-和β-芳基糖苷（NMR≥19：1）。糖基中C -3位置的构型决定了所需产物的端基异构体选择性（即α或β）。 在温和的条件下，在亚硝酸叔丁酯和HBF 4水溶液存在下，由糖和苯胺实现钯催化的一锅合成2,3-脱氧-3-酮芳基C-糖苷。这种一锅法在室温下以高收率立体地提供α-和β-芳基糖苷（NMR≥19：1）。糖基中C -3位置的构型决定了所需产物的端基异构体选择性（即α或β）。

  DOI：

  10.1055/s-0037-1611916
• 作为产物：
  描述：

  2,3,4-tri-O-acetyl-L-rhamnopyranosyl bromide 在 甲醇 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium methylate 、 sodium hexamethyldisilazane 、 戴斯-马丁氧化剂 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 aq. phosphate buffer 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.02h， 生成 (2S,3S)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one
  参考文献：
  名称：

  Automated, Multistep Continuous‐Flow Synthesis of 2,6‐Dideoxy and 3‐Amino‐2,3,6‐trideoxy Monosaccharide Building Blocks

  摘要：

  AbstractAn automated continuous flow system capable of producing protected deoxy‐sugar donors from commercial material is described. Four 2,6‐dideoxy and two 3‐amino‐2,3,6‐trideoxy sugars with orthogonal protecting groups were synthesized in 11–32 % overall yields in 74–131.5 minutes of total reaction time. Several of the reactions were able to be concatenated into a continuous process, avoiding the need for chromatographic purification of intermediates. The modular nature of the experimental setup allowed for reaction streams to be split into different lines for the parallel synthesis of multiple donors. Further, the continuous flow processes were fully automated and described through the design of an open‐source Python‐controlled automation platform.

  DOI：

  10.1002/anie.202109887

文献信息

• Base Induced Chiral Substituted Furans and Imidazoles from Carbohydrate-Derived 2-Haloenones
  作者：Kanchan Mal、Indrajit Das

  DOI：10.1021/acs.joc.5b02500

  日期：2016.2.5

  optically active (poly)hydroxy furans and imidazoles containing multiple stereocenters with good yield and excellent regioselectivity. The furan intermediates provide efficient access to synthetically valuable substituted α-benzyloxyvinyl ketones. The NMR spectrum of the substituted 2-methylfurans shows an unusual long-range (5JH–H) 1H–1H COSY cross-peak between C2–CH3 and C4–H signals.

  手性取代的呋喃和咪唑是获得生物学上重要分子的关键中间体。我们在本文中描述了在环境温度下利用K 2 CO 3 / DMSO用1,3-二羰基化合物或am形成2-卤代烯酮的无催化剂/配体的级联迈克尔型加成/分子内环化/碳水化合物环的开环反应，提供了一种直接的方法多种具有多个立体中心的旋光性（聚）羟基呋喃和咪唑，具有良好的收率和优异的区域选择性。呋喃中间体可以有效地获得合成上有价值的取代α-苄氧基乙烯基酮。取代的2-甲基呋喃的NMR光谱显示出异常的远距离（5 J H–H）1H- 1 ħ℃之间的COSY交叉峰2 -CH 3和C 4 -H信号。
• Simple oxidation of 3-O-silylated glycals: application in deblocking 3-O-protected glycals
  作者：Andreas Kirschning、Ulrike Hary、Claus Plumeier、Monika Ries、Lars Rose

  DOI：10.1039/a807479h

  日期：——

  A high yielding allylic oxidation of 3-O-silylated glycals 5–10 with the reagent system PhI(OAc)2–TMSN3 is presented. The iodine(III) species generated under these conditions is a lot more effective for generating carbohydrate-derived 3-trialkylsiloxy-2,3-dihydro-4H-pyran-4-ones 11–15 than is [hydroxy(tosyloxy)iodo]benzene, the Koser reagent. Even disaccharide 9 containing the oxidation-labile phenylseleno group is smoothly oxidized to the corresponding enone 15. The hypervalent azido iodine reagent is complementary to the Koser reagent, because 3-O-benzylated or -acylated glycals cannot be oxidized. When the iodine(III)-mediated oxidation of 3-O-silylated or -benzylated glycals is followed by a reduction step, the formal 3-O-deblocking of glycals is achieved. In particular, the Luche reduction of enones obtained from the oxidation of lyxo-configured glycals 24 and 26 is highly selective and exclusively affords the corresponding lyxo-configured glycals 28 and 30. In some cases, these products can be transformed under Mitsunobu conditions into glycals with inverted configuration at C-3 in moderate yield.

  提出了一种高产率的3-O-硅烷化糖醇5–10的烯丙氧化反应，使用的试剂系统为PhI(OAc)2–TMSN3。在这些条件下生成的碘(III)物种相比于Koser试剂[羟基(托芳基羟基)碘]苯，更有效地生成以碳水化合物为基础的3-三烷基硅氧基-2,3-二氢-4H-吡喃-4-酮11–15。即使是含有易氧化的苯基硒基的二糖9，也能平稳地氧化成相应的烯酮15。超价的叠氮碘试剂与Koser试剂互补，因为3-O-苄基化或-酰基化的糖醇无法被氧化。当3-O-硅烷化或-苄基化的糖醇进行碘(III)介导的氧化后再进行还原步骤时，可以实现糖醇的形式性3-O-去堵功能。特别是，从lyxo构型的糖醇24和26氧化得到的烯酮进行Luche还原反应时，选择性极高，专门生成相应的lyxo构型的糖醇28和30。在某些情况下，这些产物可以在Mitsunobu条件下转化为C-3配置反转的糖醇，且产率适中。
• Addition of C-nucleophiles to carbohydrate-derived 2,3-dihydro-4H-pyran-4-ones: A new entry to thromboxane analogues
  作者：Andreas Kirschning、Jan Harders

  DOI：10.1016/s0040-4020(97)00475-4

  日期：1997.6

  Nucleophilic additions of silyl- and sulfur-stabilized carbanions 5a-c to carbohydrate-derived 2,3-dihydro-4H-pyran-4-ones 4a,b are described. Depending on the combination of substituents attached to the C1-anion, either 1,2- or 1,4-adducts are preferentially formed. Coupling of vinyl cuprate derived from 16 with enone 4a stereoselectively afforded pyranone 17 which is a potential precursor for thromboxane

  描述了甲硅烷基和硫稳定的碳负离子5a-c向碳水化合物衍生的2,3-二氢-4H-吡喃-4-酮4a，b的亲核加成。根据与C 1-阴离子连接的取代基的组合，优先形成1,2-或1,4-加合物。衍生自16的烯丙基铜的乙酸铜与烯酮4a立体选择性地提供了吡喃酮17，其是血栓烷类似物的潜在前体。
• Palladium‐Catalyzed Reaction of Aryl Iodides and Glycal Enones: Application in the Preparation of Dapagliflozin Analogues
  作者：Adesh Kumar Singh、Rapelly Venkatesh、Vimlesh Kumar Kanaujiya、Varsha Tiwari、Jeyakumar Kandasamy

  DOI：10.1002/ejoc.202200023

  日期：2022.9.6

  A wide range of aryl iodides bearing electron-donating and withdrawing groups underwent oxidative C-1 arylation with enones derived from glycals in the presence of Pd(OAc)2 and AgNO3 under ligand-free conditions. The developed methodology was successfully applied in the preparation of dapagliflozin analogues (SGLT-2 inhibitor).

  在无配体条件下，在 Pd(OAc) 2和 AgNO 3存在下，各种带有给电子基团和吸电子基团的芳基碘化物与衍生自糖醛的烯酮发生氧化C -1 芳基化。所开发的方法成功地应用于制备达格列净类似物（SGLT-2 抑制剂）。
• Development of Routes for the Stereoselective Preparation of β-Aryl-<i>C</i>-glycosides via <i>C</i>-1 Aryl Enones
  作者：Adesh Kumar Singh、Vimlesh Kumar Kanaujiya、Varsha Tiwari、Shahulhameed Sabiah、Jeyakumar Kandasamy

  DOI：10.1021/acs.orglett.0c02843

  日期：2020.10.2

  various arylboronic acids bearing electron-donating and -withdrawing groups in the presence of palladium acetate and 1,10-phenanthroline. These reactions provided synthetically useful C-1 aryl enones in good yields. Many sensitive functional groups as well as protecting groups present in arylboronic acids and enones, respectively, remained intact under optimized conditions. The stereoselective hydrogenation

  宽范围的烯酮衍生自d -glucal，d -galactal，升-rhamnal，d -rhamnal，和升-arabinal后行与各种芳基硼酸轴承供电子和在乙酸钯的存在吸电子基团的Heck耦合和1,10-菲咯啉。这些反应以良好的产率提供了合成上有用的C -1芳基烯酮。在优化的条件下，芳基硼酸和烯酮中分别存在的许多敏感官能团和保护基团保持完整。C -1芳基烯酮与Pd-C / H 2的立体选择性加氢提供2-脱氧芳基-C的β-异构体-糖苷具有优异的产率。所述C- 1芳基烯酮也被用来作为用于2-羟基β -芳基-的合成前体Ç -glycosides。以优异的产率实现了C -1芳基烯酮的区域选择性C -2卤化和乙烯基化。