4-t-butylphenyl4, 6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside | 171082-23-8

• 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: 4-t-butylphenyl4, 6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
• 英文别名: [(2R,3S,6R)-3-acetyloxy-6-(4-tert-butylphenoxy)-3,6-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 171082-23-8
• 化学式: C₂₀H₂₆O₆
• 分子量: 362.423
• InChiKey: YYVCZNKMKQVOKO-OTWHNJEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-t-butylphenyl4, 6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 咪唑 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 p-tert-Butylphenyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds

  摘要：

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.

  DOI：

  10.1021/jo961881o
• 作为产物：
  描述：

  (2R,3S,6R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-[(2-methylpropan-2-yl)oxy]-3,6-dihydro-2H-pyran-3-ol 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 4-t-butylphenyl4, 6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds

  摘要：

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.

  DOI：

  10.1021/jo961881o

文献信息

• Magnetic Core-Shell Fe3O4@C-SO3H as an Efficient and Renewable ‘Green Catalyst’ for the Synthesis of O-2,3-Unsaturated Glycopyranosides
  作者：Jianbo Zhang、Guosheng Sun、Saifeng Qiu、Zekun Ding、Heshan Chen、Jiafen Zhou、Zhongfu Wang

  DOI：10.1055/s-0036-1588891

  日期：——

  rearrangement. The donors include 3,4,6-tri-O-acetyl- d -glucal and 3,4-di-O-acetyl- l -rhamnal. The acceptors consist of primary alcohols, secondary alcohols, tert-butanol, unsaturated alcohols, halogenated alcohol, sterol, sugars, and phenols. O-2,3-Unsaturated glycosides were obtained rapidly ( 5:1 to 19:1). Moreover, the catalyst can be easily separated from the reaction with an external magnetic force

  研究了一种磁性核壳固体酸催化剂 Fe3O4@C-SO3H，用于通过费里叶重排合成 O-2,3-不饱和糖苷。供体包括3,4,6-三-O-乙酰-d-葡糖醛和3,4-二-O-乙酰-1-鼠李醛。受体由伯醇、仲醇、叔丁醇、不饱和醇、卤代醇、甾醇、糖和酚组成。快速获得 O-2,3-不饱和糖苷（5:1 至 19:1）。此外，该催化剂可以很容易地通过外部磁力从反应中分离出来并重复使用至少 5 次，每次循环后产物的产率没有任何显着下降，表明它是一种很有前途的 2,3-不饱和绿色催化剂。糖苷合成。
• Synthetic Approach, Regio- and Stereochemical Characterization and Differentiation of New Potential Antioxidant C- And O-Arylglycosides
  作者：Gianluca Giorgi、Fabio Ponticelli、Laura Salvini、Antoaneta Trendafilova、Massimo Valoti、Federica Pessina

  DOI：10.1002/1099-0690(200301)2003:1<106::aid-ejoc106>3.0.co;2-7

  日期：2003.1

  two states. Mass spectrometry proved very effective for characterization of and differentiation between C- and O-isomers, as well as positional isomers. Unimolecular reactions occurring in the gas phase are specific to the chemical structures, and ion abundances can be related to their stabilities. This study has allowed the evaluation of the influences of the different linkages between the two moieties

  两个系列的具有潜在抗氧化性能的 C-和 O-芳基糖苷已被合成、表征和结构区分。对合成方法的重新研究提供了对获得的产品及其化学结构的更好的了解。已经在溶液、晶体和气相中对每种化合物进行了区域和立体化学表征和区分。在溶液中获得的数据与晶体结构之间的比较表明这两种状态的特征密切相关。质谱证明对于表征和区分 C-和 O-异构体以及位置异构体非常有效。在气相中发生的单分子反应特定于化学结构，离子丰度可能与其稳定性有关。该研究允许评估两个部分之间的不同连接和取代基位置对化合物化学性质的影响。C-异构体显示抗氧化能力，作为过氧自由基清除剂，并抑制脂质过氧化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Synthesis of α- and β-<i>C</i>-Aryl Δ²-Glycopyranosides from <i>p</i>-<i>tert</i>-Butylphenyl Δ²-Glycopyranosides via Grignard Reagents
  作者：Christophe Moineau、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo9714674

  日期：1998.2.1

  Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (1a alpha) or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1b alpha) with various functionalized arylmagnesium bromides in the presence of a catalytic amount of PdCl2(dppf) at 25 degrees C in THF afforded the corresponding unsaturated C-arylglycosides 2-14 having the ct-configuration in quite good yields. Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated alpha-C-glycosides 15-18, although in lower yields. When the same reaction was performed in the presence of NiCl2(dppe) as the catalyst at -40 degrees C, only the formation of the corresponding unsaturated C-arylglycosides having the beta-configuration was observed. As expected, reaction of phenylmagnesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-beta-D-erythro-hex-2-enopyranoside (1a beta) in the presence of NiCl2(dppe) gave only the unsaturated beta-C-phenylglycoside 2a beta, while palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2a alpha. Reaction of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside (20) afforded stereospecifically the unsaturated alpha- and beta-C-phenylglycoside 25 in the presence of PdCl2-(dppf) and NiCl2(dppe), respectively.
• An Easy and Efficient Preparation of Aryl α-<i>O</i>-Δ²−Glycosides
  作者：I. Frappa、D. Sinou

  DOI：10.1080/00397919508011424

  日期：1995.10

  Ferrier reaction between acetylglycals and p-NO2, m-NO2 and p-t-butylphenol after recrystallization gave aryl O-Delta(2)-glycosides as the pure a anomers. Deacetylation of these compounds and benzylation of the crude diol led to the corresponding aryl alpha-O-Delta(2)-4,6-di-O-benzylglycosides in large amounts.