phenyl 2,3,4,6-tetra-O-benzyl-1-seleno-β-D-glucopyranoside | 139903-49-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4,6-tetra-O-benzyl-1-seleno-β-D-glucopyranoside
• 英文别名: (2R,3R,4S,5R,6S)-3,4,5-tris(phenylmethoxy)-2-(phenylmethoxymethyl)-6-phenylselanyloxane
• CAS: 139903-49-4
• 化学式: C₄₀H₄₀O₅Se
• 分子量: 679.715
• InChiKey: QAMDKTXBECVVKY-DTQLOPILSA-N

物化性质

• 熔点：
  78-79 °C(Solv: ethanol (64-17-5))
• 沸点：
  742.8±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.71
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-1-seleno-β-D-glucopyranoside 在 titanium(IV) isopropylate 叔丁基过氧化氢 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到2,3,4,6-tetra-O-benzyl 1,5-anhydro-D-arabino-hex-1-enitol
  参考文献：
  名称：

  消除糖基亚硒酸盐的反应

  摘要：

  糖苷亚硒酸酯是通过Sharpless型氧化从硒代糖苷原位生成的，可以轻松地进行syn消除，从而以高收率得到2-羟基和2-氨基糖基。

  DOI：

  10.1016/j.tet.2004.07.005
• 作为产物：
  描述：

  β-D-葡萄糖五乙酸酯 在 三氟化硼乙醚 、 sodium methylate 、 次磷酸 、 sodium hydride 作用下， 以 甲醇 为溶剂， 反应 23.5h， 生成 phenyl 2,3,4,6-tetra-O-benzyl-1-seleno-β-D-glucopyranoside
  参考文献：
  名称：

  Novel glycosidation methodology. The use of phenyl selenoglycosides as glycosyl donors and acceptors in oligosaccharide synthesis

  摘要：

  The use of phenyl selenoglycosides as glycosyl donors and acceptors in glycosidation reactions is described. The versatility of these novel compounds is illustrated by the selective activation of both ''disarmed'' and ''armed'' phenyl selenoglycoside donors over ''armed'' ethyl thioglycoside acceptors with silver trifluoromethanesulfonate in the presence of potassium or silver carbonate to give disaccharides in excellent yield. Selective activation of glycosyl bromide donors over phenyl selenoglycoside acceptors is realized by silver trifluoromethanesulfonate promotion in the presence of collidine. Such selectivity is also demonstrated by the activation of a glycosyl trichloroacetimidate donor in the presence of selenoglycoside acceptors with triethylsilyl trifluoromethanesulfonate. The central role of selenoglycosides is illustrated by the synthesis of a trisaccharide that profits from the sequential, selective activation of a glycosyl bromide donor over a selenoglycoside acceptor and the resulting disaccharide selenoglycoside over a thioglycoside acceptor. The liberation of the anomeric hydroxyl group from a phenyl selenoglycoside is also described.

  DOI：

  10.1021/jo00064a012

文献信息

• Selective electrochemical glycosylation by reactivity tuning1
  作者：Robert R. France、Richard G. Compton、Benjamin G. Davis、Antony J. Fairbanks、Neil V. Rees、Jay D. Wadhawan

  DOI：10.1039/b316728c

  日期：——

  Electrochemical glycosylation of a selenoglycoside donor proceeds efficiently in an undivided cell in acetonitrile to yield β-glycosides. Measurement of cyclic voltammograms for a selection of seleno-, thio-, and O-glycosides indicates the dependence of oxidation potential on the anomeric substituent allowing the possibility for the rapid construction of oligosaccharides by selective electrochemical activation utilising variable cell potentials in combination with reactivity tuning of the glycosyl donor. A variety of disaccharides are readily synthesised in high yield, but limitations of the use of selenoglycosides as glycosyl donors for selective glycosylation of thioglycoside acceptors are exposed. The first electrochemical trisaccharide synthesis is described.

  在丙酮腈中，未分割电池内的电化学糖基化过程有效地进行，以硒糖供体生成β-糖苷。通过对一系列硒、硫和氧糖苷的循环伏安图测量，表明氧化电位依赖于异头取代基，从而可以通过选择性电化学活化，利用可变电池电位结合糖基供体反应性调节，快速构建寡糖。多种二糖可轻松合成，产率较高，但使用硒糖苷作为糖基供体，在选择性糖基化硫糖苷受体方面存在局限性。首次报道了电化学三糖合成。
• 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。
• Contrasting reactivity of thioglucoside and selenoglucoside donors towards promoters: implications for glycosylation stereocontrol
  作者：Renate M. van Well、Tiina S. Kärkkäinen、K.P. Ravindranathan Kartha、Robert A. Field

  DOI：10.1016/j.carres.2006.04.029

  日期：2006.7

  The stereochemical outcome of glycosylation reactions with model thioglycosides and selenoglycosides proved to be dependent on the source of promoter iodonium ion, with iodine giving different results to N-iodosuccinimide (NIS) alone or N-iodosuccinimide/trimethylsilyltrifluoromethanesulfonate (NIS/TMSOTf). In contrast to armed thioglycosides, which anomerise, and disarmed thioglycosides, which do not

  模型硫代糖苷和硒代糖苷的糖基化反应的立体化学结果被证明取决于促进剂碘鎓离子的来源，碘对单独的 N-碘代琥珀酰亚胺 (NIS) 或 N-碘代琥珀酰亚胺/三甲基硅基三氟甲磺酸酯 (NIS/TMSOTf) 产生不同的结果。与异构化的武装硫代糖苷和不反应的解除武装硫代糖苷相反，武装和解除武装的硒代糖苷在与碘反应时都会产生相应的糖基碘化物。此外，虽然单电子转移剂 DDQ 单独是一种无效的促进剂，但与碘组合时，与六氯锑酸三（4-溴苯基）铵（BAHA）相比，它对硫代糖苷和硒代糖苷产生更好的乙腈辅助 β 立体选择性。
• 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。
• Catalytic and Photochemical Strategies to Stabilized Radicals Based on Anomeric Nucleophiles
  作者：Feng Zhu、Shuo-qing Zhang、Zhenhao Chen、Jinyan Rui、Xin Hong、Maciej A. Walczak

  DOI：10.1021/jacs.0c03298

  日期：2020.6.24

  metal-free conditions where a disulfide initiator can be activated by a Lewis base additive. Both strategies utilize anomeric nucleophiles as efficient radical donors and achieve a switch from an ionic to a radical pathway. Taken together, the stability of glycosyl nucleophiles, a broad substrate scope, and high anomer-ic selectivities observed for the thermal and photochemical protocols make this novel

  碳水化合物是生物体的三大主要大分子之一，在细胞间通讯、细胞识别和免疫活性等各种生物过程中发挥着重要作用。虽然大多数已建立的通过异头碳安装碳水化合物的方法依赖于亲核置换，但异头自由基因其官能团相容性和高异头选择性而代表了一种有吸引力的替代方案。在此，我们证明了通过将 Cu(I) 催化与蓝光照射合并以实现高度立体选择性的 C(sp3)-S 交叉偶联反应，可以将 C1 锡烷等异头亲核试剂转化为异头自由基。机理研究和 DFT 计算表明，CS 键形成步骤是通过将异头自由基直接转移到与 Cu(II) 物质结合的硫亲电子试剂而发生的。该途径补充了在无金属条件下观察到的自由基链，其中二硫化物引发剂可以被路易斯碱添加剂活化。这两种策略都利用异头亲核试剂作为有效的自由基供体，并实现了从离子途径到自由基途径的转变。总之，糖基亲核试剂的稳定性、广泛的底物范围以及在热和光化学方案中观察到的高异头选择性使得这种新型 CS