phenyl 1-seleno-β-D-glucopyranoside | 4981-97-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 1-seleno-β-D-glucopyranoside
• 英文别名: phenyl-1-seleno-β-D-glucopyranoside；phenyl-β-selenoglucoside；phenyl-(1-seleno-β-D-glucopyranoside)；Phenyl-(1-seleno-β-D-glucopyranosid)；(2R,3S,4S,5R,6S)-2-(hydroxymethyl)-6-phenylselanyloxane-3,4,5-triol
• CAS: 4981-97-9
• 化学式: C₁₂H₁₆O₅Se
• 分子量: 319.216
• InChiKey: NCQGFMOVCHVEME-ZIQFBCGOSA-N

物化性质

• 熔点：
  107.5-108.0 °C(Solv: isopropanol (67-63-0))
• 沸点：
  515.0±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.18
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  90.2
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phenyl 1-seleno-β-D-glucopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 sodium hydride 、 氘代三正丁基锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 3.0h， 生成 1-deoxy-D-glucose tetraacetate
  参考文献：
  名称：

  以构象受限的葡萄糖衍生物为底物，研究异头自由基反应中的构象-异头作用-立体选择性关系。

  摘要：

  我们先前的理论认为，由于异头自由基反应的立体选择性受到动力学异头作用的显着影响，可以通过限制自由基中间体的构象来控制，因此底物吡喃糖环的适当构象限制将使α -和β-立体选择性异头自由基反应是可能的。该理论基于我们先前以d-木糖衍生物为底物的端基自由基反应的结果。我们在本文中报道了构象受限的1-苯基硒代d-葡萄糖衍生物2g和3g（受O环双缩酮部分限制在（4）C（1）-构象中）和4g，5g的异头自由基氘化反应。 6g，7g和8g受庞大的O-甲硅烷基保护基团限制在（1）C（4）构象中。使用（4）C（1）限制的底物2g和3g，用Bu（3）SnD进行的自由基氘化可高度立体选择性地提供相应的alpha产物（alpha / beta = 98：2），而（1）C （4）-限制的底物6g具有在5位上的三角形（sp（2））碳取代基，即-CHO，选择性地产生β-产物（α/β＝ 0：100）。因此，立体选择性由于

  DOI：

  10.1021/jo030128+
• 作为产物：
  描述：

  苯硒酚 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 phenyl 1-seleno-β-D-glucopyranoside
  参考文献：
  名称：

  Total synthesis of the Glc3Man N-glycan tetrasaccharide

  摘要：

  The total synthesis of the tetrasaccharide Glcalpha(1-->2)Glcalpha(1-->3)Glcalpha(1-->3)ManalphaOMe, which corresponds to the terminal tetrasaccharide portion of the glucose terminated arm of the N-glycan tetradecasaccharide, was achieved by the use of differentially protected selenoglycosides and thioglycosides as glycosyl donors, all of which possessed non-participating protection of the 2-hydroxyl group. Favourable anomeric stereoselectivity was achieved for the glycosylation reactions by the use of ether as solvent, or co-solvent. Global deprotection by catalytic hydrogenation with palladium acetate in a mixture of ethanol and acetic acid yielded the target tetrasaccharide. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)01221-8

文献信息

• [EN] SELENO-COMPOUNDS AND THERAPEUTIC USES THEREOF<br/>[FR] COMPOSÉS SÉLÉNO ET LEURS UTILISATIONS THÉRAPEUTIQUES
  申请人：UNIV MELBOURNE

  公开号：WO2012054988A1

  公开（公告）日：2012-05-03

  The present invention relates to compounds and compositions useful as antioxidants and in particular to selenium containing compounds of formula (I): wherein n is 1, 2, or 3; m is 2, 3, 4, or 5; and each R] is independently -(optionally substituted C 1 -C3 alkylene) p-OH, where p is 0 or 1, or a salt thereof. The invention also relates to the use of these seleno-compounds in the treatment of diseases or conditions associated with increased levels of oxidants produced by myeloperoxidase (MPO), such as for instance, atherosclerosis.

  本发明涉及作为抗氧化剂有用的化合物和组合物，特别是公式(I)中含硒的化合物，其中n为1、2或3；m为2、3、4或5；每个R]独立地为-(可选择地取代的C1-C3烷基) p-OH，其中p为0或1，或其盐。该发明还涉及在治疗由髓过氧化物酶(MPO)产生的氧化剂水平增加引起的疾病或症状中使用这些硒化合物，例如动脉粥样硬化。
• Regioselective lipase-catalysed acylation of 4,6-O-benzylidene-α- and-β-d-pyranoside derivatives displaying a range of anomeric substituents
  作者：Jonathan J. Gridley、Andrew J. Hacking、Helen M.I. Osborn、David G. Spackman

  DOI：10.1016/s0040-4020(98)00935-1

  日期：1998.12

  The application of Lipase enzymes to effect regioselective C-3-O-acylation of - and -galactopyranosides displaying a range of anomeric substituents, and C-2-O-acylation of phenyl and ethyl is reported. In particular this method has allowed introduction of a variety of acyl protecting groups at the C-3 hydroxyl group of ethyl 11.

  脂肪酶的到应用的效果的区域选择性C-3- Ö的酰化-和-galactopyranosides显示范围的端基异构体的取代基，和C-2- Ö苯基的酰化和乙基报道。特别地，该方法允许在乙基11的C-3羟基处引入各种酰基保护基。
• Selective activation of glycosyl donors utilising electrochemical techniques: a study of the thermodynamic oxidation potentials of a range of chalcoglycosides
  作者：Robert R. France、Neil V. Rees、Jay D. Wadhawan、Antony J. Fairbanks、Richard G. Compton

  DOI：10.1039/b316720h

  日期：——

  A series of six chalcoglycosides (phenyl-2,3,4,6-tetra-O-benzoyl-1-seleno-β-D-glucopyranoside, phenyl-2,3,4,6-tetra-O-benzyl-1-seleno-β-D-glucopyranoside, phenyl-2,3,4,6-tetra-O-benzyl-1-thio-β-D-glucopyranoside, p-tolyl-2,3,4,6-O-benzoyl-1-thio-β-D-glucopyranoside, p-tolyl-2,3,4,6-O-benzyl-1-thio-β-D-glucopyranoside, and phenyl-2,3,4,6-O-benzyl-β-D-glucopyranoside) are voltammetrically interrogated in dimethyl sulfoxide, so as to determine their formal (i.e. thermodynamic) redox potentials. The electrochemical oxidation of the chalcoglycoside is shown to follow an overall EC-type mechanism, in which the electro-generated cation radical undergoes an irreversible carbon–chalcogen bond rupture to produce the corresponding glycosyl cation, which may react further. The kinetics of the initial heterogeneous electron transfer process and subsequent irreversible homogeneous chemical degradation of the radical cation are reported, with values for the standard electrochemical rate constant k0 in the order of 10−2 cm s−1 and the first order homogeneous rate constant, k1, of the order of 103 s−1. The formal oxidation potentials were found to vary according to the identity of the chalcogenide, such that OPh > SPh ∼ STol > SePh.

  一系列六个硫醇糖苷（苯基-2,3,4,6-四-O-苯甲酰基-1-硒-β-D-吡喃葡糖苷，苯基-2,3,4,6-四-O-苄基-1-硒-β-D-吡喃葡糖苷，苯基-2,3,4,6-四-O-苄基-1-硫-β-D-吡喃葡糖苷，对甲苯基-2,3,4,6-O-苯甲酰基-1-硫-β-D-吡喃葡糖苷，对甲苯基-2,3,4,6-O-苄基-1-硫-β-D-吡喃葡糖苷，以及苯基-2,3,4,6-O-苄基-β-D-吡喃葡糖苷）在二甲基亚砜中通过伏安法进行检测，以确定它们的正式（即热力学）氧化还原电位。实验表明，硫醇糖苷的电化学氧化遵循一个总体的EC型机理，其中电生成的阳离子自由基经历不可逆的碳-硫键断裂，产生相应的苷阳离子，该苷阳离子可能进一步反应。报道了初始的非均相电子转移过程及其后不可逆的均相自由基阳离子化学降解的动力学，其中标准电化学速率常数k0约为10^-2 cm s^-1，一级均相速率常数k1约为10^3 s^-1。发现正式氧化电位根据硫醇基团的身份而变化，顺序为OPh > SPh ∼ STol > SePh。
• Stereoretentive Reactions at the Anomeric Position: Synthesis of Selenoglycosides
  作者：Feng Zhu、Sloane O'Neill、Jacob Rodriguez、Maciej A. Walczak

  DOI：10.1002/anie.201802847

  日期：2018.6.11

  Reported is the stereospecific cross‐coupling of anomeric stannanes with symmetrical diselenides, resulting in the synthesis of selenoglycosides with exclusive anomeric control. The reaction proceeds without the need for directing groups and is compatible with free hydroxy groups as demonstrated in the preparation of glycoconjugates derived from mono‐, di‐, and trisaccharides and peptides (35 examples)

  报道了异头锡烷与对称二硒化物的立体特异性交叉偶联，从而合成了具有独家异头控制的硒糖苷。该反应无需定向基团即可进行，并且与游离羟基相容，如从单糖、二糖和三糖和肽衍生的糖缀合物的制备中所证明的（35 个示例）。鉴于其普遍性和广泛的底物范围，本文介绍的糖基交叉偶联方法可用于合成含硒糖模拟物和糖缀合物。
• Convenient syntheses of 1,2-trans selenoglycosides using isoselenuronium salts as glycosylselenenyl transfer reagents
  作者：Ambati Ashok Kumar、Tünde Zita Illyés、Katalin E. Kövér、László Szilágyi

  DOI：10.1016/j.carres.2012.07.012

  日期：2012.10

  temperature to afford the corresponding selenoglycosides in good yields. Aryl halides react to appreciable extent only if bearing activating nitro groups on the aromatic ring. Reactions with acylating reagents such as acetic anhydride and benzoyl chlorides furnished anomeric selenoesters some of which were recently proposed as starting compounds for alternative selenoglycoside syntheses. Selenodisaccharides

  可以在一个高收率的步骤中从乙酰卤代糖制得的诸如三和四的Se-糖基-异亚硒酸铵盐被证明是用于合成多种硒代糖苷的方便的起始原料。与（芳）烷基卤化物的反应在温和的条件下，在室温下，在短时间内在室温下进行，以良好的收率得到相应的硒代糖苷。仅当芳族环上带有活化硝基时，芳基卤化物才会发生明显的反应。与酰化试剂如乙酸酐和苯甲酰氯的反应提供了端粒的硒酸酯，最近提出了其中的一些作为替代硒代糖苷合成的起始化合物。