(+)-(2S,3R)-3-(Benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one | 56733-55-2

• 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,3R)-3-(Benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one
• 英文别名: (2S,3R)-3-(benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one；(2S,3R)-2-methyl-3-phenylmethoxy-2,3-dihydropyran-4-one
• CAS: 56733-55-2
• 化学式: C₁₃H₁₄O₃
• 分子量: 218.252
• InChiKey: RVCHBHBGYLNRKV-GXFFZTMASA-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,3R)-3-(Benzyloxy)-2-methyl-2,3-dihydro-4H-pyran-4-one 在 甲醇 、 sodium tetrahydroborate 、 caesium carbonate 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 生成 4-O-benzyl-1-adamantanethiol-β-L-boivinose
  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
• 作为产物：
  描述：

  L-fucal 在 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium hexamethyldisilazane 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.53h， 生成 (+)-(2S,3R)-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。
• Rapid <i>de Novo</i> Preparation of 2,6-Dideoxy Sugar Libraries through Gold-Catalyzed Homopropargyl Orthoester Cyclization
  作者：Subbarao Yalamanchili、William Miller、Xizhao Chen、Clay S. Bennett

  DOI：10.1021/acs.orglett.9b03812

  日期：2019.12.6

  A flexible de novo route capable of producing libraries of 2,6-dideoxy sugars is described. We have found that Au(JackiePhos)SbF6MeCN promotes the conversion of homopropargyl orthoesters into functionalized 2,3-dihydro-4H-pyran-4-ones in good to excellent yields (71-90%). These latter compounds can be easily converted into a number of otherwise difficult to access 2,6-dideoxy sugars.

  描述了一种能够产生 2,6-二脱氧糖文库的灵活的从头路线。我们发现 Au(JackiePhos)SbF6MeCN 可以促进均炔丙基原酸酯转化为功能化 2,3-二氢-4H-吡喃-4-酮，产率从良好到优异 (71-90%)。后面这些化合物可以很容易地转化为许多原本难以获得的 2,6-二脱氧糖。
• Gold(III) Chloride Catalyzed Synthesis of Chiral Substituted 3-Formyl Furans from Carbohydrates: Application in the Synthesis of 1,5-Dicarbonyl Derivatives and Furo[3,2-<i>c</i>]pyridine
  作者：Kanchan Mal、Abhinandan Sharma、Indrajit Das

  DOI：10.1002/chem.201402286

  日期：2014.9.8

  This report describes a gold(III)‐catalyzed efficient general route to densely substituted chiral 3‐formyl furans under extremely mild conditions from suitably protected 5‐(1‐alkynyl)‐2,3‐dihydropyran‐4‐one using H2O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne–gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti‐endo‐dig

  本报告介绍了一种金（III）催化的有效一般路线，该路线可在极其温和的条件下，使用H 2 O作为适当保护的5-（1-炔基）-2,3-二氢吡喃-4-酮，从密集的手性3-甲酰基呋喃中合成。亲核试剂。该反应通过初始形成活化的炔烃-金（III）复杂中间体而进行，然后发生多米诺亲核攻击/反内切环化，或形成环氧鎓离子并随后被H 2 O攻击。为了确认拟议的机理途径，我们如预期的那样使用MeOH代替H 2 O作为亲核试剂，生成取代的呋喃[3,2- c ]吡喃衍生物。相似的furo [3,2‐ c还可以通过重铬酸吡啶鎓（PDC）氧化取代的手性3-甲酰基呋喃来制备具有杂合碳水化合物-呋喃衍生物的] pyran骨架。按照氧化，碘化和Sonogashira偶联顺序，可以从单糖（己糖和戊糖）合成相应的受保护的5-（1-炔基）-2-3-二氢吡喃-4-酮。此外，为证明手性3-甲酰基呋喃衍生物的潜力，已证明这些衍生物的TiBr
• Oxidation of Fully Protected Glycals by Hypervalent Iodine Reagents
  作者：Andreas Kirschning

  DOI：10.1021/jo00110a028

  日期：1995.3

  A new application of organoiodine(III) is presented. Fully protected glycals are directly converted into 2,3-dihydro-4H-pyran-4-ones by [hydroxy(tosyloxy)iodo]benzene (PhI(OH)OTs, 1). The detailed study reveals that this conversion is independent of the relative stereochemistry as well as the nature of protection on the pyran ring. 3-O-Silyl groups are most smoothly converted into the keto group giving 2,3-dihydro-4H-pyran-4-ones in yields up to 74%. In contrast, 4,6-di-O-acetyl-3-deoxyglucal (19) affords the rearranged oxidation product 32. Both observations can be reconciled by the proposed mechanism.