phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-mannopyranoside

• 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-thio-β-D-mannopyranoside
• 英文别名: phenyl 2,3,4,6-tri-O-benzyl-1-thio-β-D-mannopyranoside；(2R,3R,4S,5S,6S)-3,4,5-tris(phenylmethoxy)-2-(phenylmethoxymethyl)-6-phenylsulfanyloxane
• 化学式: C₄₀H₄₀O₅S
• 分子量: 632.821
• InChiKey: IKCMSYGNAFDJNX-LVZHEHNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 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：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-mannopyranoside 、 2-(环丙基乙炔基)苯甲酸 在 辛酸铑 、 methyl 2-(4-chlorophenyl)-2-diazoacetate 、 2,6-二叔丁基-4-甲基吡啶三氟甲磺酸盐 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以95%的产率得到2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl ortho-(cyclopropylethynyl)benzoate
  参考文献：
  名称：

  通过连续的铑 (II) 和布朗斯台德酸催化实现糖基化

  摘要：

  在此，我们报道了一种高效的糖基化反应，包括两个按时间顺序精心设计的催化循环：1）铑催化形成锍叶立德；2) Brønsted 酸催化形成锍离子。该协议强调了一种有效且稳健的策略，可从适合糖基化的糖基锍叶立德前体制备糖基锍离子。

  DOI：

  10.1021/jacs.9b04619
• 作为产物：
  描述：

  Phenyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 sodium hydride 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 5.0h， 生成 phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-mannopyranoside
  参考文献：
  名称：

  剖析控制硫代葡萄糖苷和硫代甘露糖苷反应性的作用†

  摘要：

  在NIS / TfOH活化下，在葡萄糖和甘露聚糖配置的硫糖苷中研究了相邻基团的作用。将具有2- O-苯甲酰基的施主与具有参与性中性2- O-苄基的施主进行比较，所述施主具有能够（1,2-反式）和不能（1,2-顺式）发挥亲核作用。通过使用糖基供体组之间的竞争实验，邻近基团参与的直接效应和2- O的电子吸收效应-苯甲酰基可被分离。该研究使人们深入了解了1和2位的立体化学，以及糖苷配基的性质（Ph或Et）如何对糖基供体的反应性产生显着影响。

  DOI：

  10.1039/c7ob02968c

文献信息

• 2′-Carboxybenzyl glycosides: glycosyl donors for C-glycosylation and conversion into other glycosyl donors
  作者：Yong Joo Lee、Ju Yuel Baek、Bo-Young Lee、Sung Soo Kang、Hye-Seo Park、Heung Bae Jeon、Kwan Soo Kim

  DOI：10.1016/j.carres.2006.03.014

  日期：2006.7

  Glycosylation of various glycosyl acceptors with 2'-carboxybenzyl (CB) 2,3,4,6-tetra-O-benzyl-beta-D-glucopyranoside and CB 2,3,4,6-tetra-O-benzyl-alpha-D-mannopyranoside as glycosyl donors afforded alpha-C-glycosides exclusively or predominantly in good yields. CB glycosides were also converted to other well-known glycosyl donors, the corresponding phenyl thioglycoside and the glycosyl fluoride derivatives

  各种糖基受体与2'-羧基苄基（CB）2,3,4,6-四-O-苄基-β-D-吡喃葡萄糖苷和CB 2,3,4,6-四-O-苄基-α-的糖基化D-甘露糖吡喃糖苷作为糖基供体仅或主要以良好的收率提供了α-C-糖苷。CB糖苷也被转化为其他众所周知的糖基供体，相应的苯基硫代糖苷和糖基氟化物衍生物。
• Anomeric Thioglycosides Give Different Anomeric Product Distributions under NIS/TfOH Activation
  作者：Helle H. Trinderup、Tatjana L. P. Sandgaard、Line Juul-Madsen、Henrik H. Jensen

  DOI：10.1021/acs.joc.1c03001

  日期：2022.3.18

  The reaction of a series of anomeric thioglycosides with various glycosyl acceptors and N-iodosuccinimide/catalytic triflic acid was investigated with respect to reactivity and anomeric selectivity. In general, β-configured donors were found to give a more β-selective reaction outcome compared to their α-configured counterparts. The relative reactivity of various thioglycosides was measured through

  研究了一系列异头硫苷与各种糖基受体和N-碘代琥珀酰亚胺/催化三氟甲磺酸的反应的反应性和异头选择性。一般而言，发现 β 配置的供体与其 α 配置的对应物相比，会产生更多的 β 选择性反应结果。通过竞争实验测量了各种硫糖苷的相对反应性，确定了以下顺序：苯基、甲苯基、甲基、乙基、异丙基和1-金刚烷基。
• Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions
  作者：Jasper Dinkelaar、Ana Rae de Jong、Robert van Meer、Mark Somers、Gerrit Lodder、Herman S. Overkleeft、Jeroen D. C. Codée、Gijsbert A. van der Marel

  DOI：10.1021/jo900662v

  日期：2009.7.17

  The stereodirecting effect of the glycosyl C-5 substituent has been investigated in a series of D-pyranosyl thioglycoside donors and related to their preferred positions in the intermediate H-3(4) and H-4(3) half-chair oxacarbenium ions. Computational studies showed that an axially positioned C-5 carboxylate ester can stabilize the (3)H4 half-chair oxacarbenium ion conformer by donating electron densit from its carbonyl function into the electron-poor oxacarbenium ion functionality. A similar stabilization can be achieved by a C-5 benzyloxyrnethyl group, but,the magnitude of this stabilization is significantly smaller than for the C-5 carboxylate ester. As a result, the preference of the C-5 benzyloxymethyl to occupy an axial position in the half-chair oxacarbenium ions is much reduced compared to the C-5 carboxylate ester. To minimize steric interactions, a C-5 methyl group prefers to adopt an equatorial position and therefore favors the H-4(3) half-chair oxacarbenium ion. When all pyranosyl substituents occupy their favored position in one of the two intermediate half-chair oxacarbenium ions, highly stereoselective glycosylations can be achieved as revealed by the excellent beta-selectivity of mannuronate esters and alpha-selectivity of 6-deoxygulosides.
• Glycosylation Enabled by Successive Rhodium(II) and Brønsted Acid Catalysis
  作者：Lingkui Meng、Peng Wu、Jing Fang、Ying Xiao、Xiong Xiao、Guangsheng Tu、Xiang Ma、Shuang Teng、Jing Zeng、Qian Wan

  DOI：10.1021/jacs.9b04619

  日期：2019.7.31

  reaction comprises two chronological meticulously-designed catalytic cycles: 1) rhodium-catalyzed formation of sulfonium ylide; 2) Brønsted acid-catalyzed formation of sulfonium ion. This protocol highlight-ed an effective and robust tactic to prepare glycosyl sulfonium ion from glycosyl sulfonium ylide precursor amenable for glycosylation.

  在此，我们报道了一种高效的糖基化反应，包括两个按时间顺序精心设计的催化循环：1）铑催化形成锍叶立德；2) Brønsted 酸催化形成锍离子。该协议强调了一种有效且稳健的策略，可从适合糖基化的糖基锍叶立德前体制备糖基锍离子。
• Dissection of the effects that govern thioglucoside and thiomannoside reactivity
  作者：Mads Heuckendorff、Lulu Teressa Poulsen、Christinne Hedberg、Henrik H. Jensen

  DOI：10.1039/c7ob02968c

  日期：——

  Neighboring group effects were investigated in gluco- and manno-configured thioglycosides under NIS/TfOH activation. Donors possessing a 2-O-benzoyl group that are capable (1,2-trans) and incapable (1,2-cis) of exerting nucleophilic push were compared with donors possessing a participatory neutral 2-O-benzyl group. By using competition experiments between sets of glycosyl donors the direct effect of

  在NIS / TfOH活化下，在葡萄糖和甘露聚糖配置的硫糖苷中研究了相邻基团的作用。将具有2- O-苯甲酰基的施主与具有参与性中性2- O-苄基的施主进行比较，所述施主具有能够（1,2-反式）和不能（1,2-顺式）发挥亲核作用。通过使用糖基供体组之间的竞争实验，邻近基团参与的直接效应和2- O的电子吸收效应-苯甲酰基可被分离。该研究使人们深入了解了1和2位的立体化学，以及糖苷配基的性质（Ph或Et）如何对糖基供体的反应性产生显着影响。