methyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside | 131089-34-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside
• 英文别名: (2R,3S,4S,5S,6S)-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-methoxyoxane-3,4,5-triol
• CAS: 131089-34-4
• 化学式: C₂₃H₃₂O₆Si
• 分子量: 432.589
• InChiKey: GZIVUJBHWFXBMB-AANPDWTMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.02
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  88.4
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside 在 2,6-二甲基吡啶 、 四丁基氟化铵 、 sodium hydride 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 1.0h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(trifluoromethanesulfonyl)-α-D-mannopyranoside
  参考文献：
  名称：

  Application of the Anomeric Samarium Route for the Convergent Synthesis of the C-Linked Trisaccharide α-d-Man-(1→3)-[α-d-Man-(1→6)]-d-Man and the Disaccharides α-d-Man-(1→3)-d-Man and α-d-Man-(1→6)-d-Man

  摘要：

  Studies are reported on the assembly of the branched C-trisaccharide, alpha-D-Man-(1-->3)-[alpha-D-Man-(1-->6)]-D-Man, representing the core region of the asparagine-linked oligosaccharides. The key step in this synthesis uses a SmI2-mediated coupling of two mannosylpyridyl sulfones to a C3,C6-diformyl branched monosaccharide unit, thereby assembling all three sugar units in one reaction and with complete stereocontrol at the two anomeric carbon centers. Subsequent tin hydride-based deoxygenation followed by a deprotection step produces the target C-trimer. In contrast to many of the other C-glycosylation methods, this approach employes intact carbohydrate units as C-glycosyl donors and acceptors, which in many instances parallels the well-studied O-glycosylation reactions. The synthesis of the C-disaccharides alpha-D-Man-(1-->3)-D-Man and alpha-D-Man-(1-->6)-D-Man is also described, they being necessary for the following conformational studies of all three carbohydrate analogues both in solution and bound to several mannose-binding proteins.

  DOI：

  10.1021/jo020339z
• 作为产物：
  描述：

  叔丁基二苯基氯硅烷 、 甲基-D-丙噻 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以98%的产率得到methyl 6-O-tert-butyldiphenylsilyl-α-D-mannopyranoside
  参考文献：
  名称：

  甘露聚糖和鼠李糖呋喃糖酶的四唑

  摘要：

  衍生自D-甘露呋喃糖和鼠李糖呋喃糖的两种对映异构体的四唑的合成提供了呋喃糖形式的碳水化合物的四唑类似物的第一个实例。D-呋喃四唑是潜在的甘露糖苷酶抑制剂，而L-鼠李糖唑可能会干扰分枝杆菌细胞壁的生物合成，并为结核和麻风病的治疗提供了策略。

  DOI：

  10.1016/0040-4039(95)01518-3

文献信息

• Palladium-Catalyzed <i>ortho</i>-C–H Glycosylation/<i>ipso</i>-Alkenylation of Aryl Iodides
  作者：Ya-Nan Ding、Wei-Yu Shi、Ce Liu、Nian Zheng、Ming Li、Yang An、Zhe Zhang、Cui-Tian Wang、Bo-Sheng Zhang、Yong-Min Liang

  DOI：10.1021/acs.joc.0c01392

  日期：2020.9.4

  This report describes the first example of palladium-catalyzed ortho-C–H glycosylation/ipso-alkenylation of aryl iodides, and the easily accessible glycosyl chlorides are used as a glycosylation reagent. The reaction is compatible with the functional groups of the substrates, and a series of C-aryl glycosides have been synthesized in good to excellent yield and with excellent diastereoselectivity.

  该报告描述了钯催化芳基碘化物邻位-C-H糖基化/ ipso-烯基化的第一个例子，并且易于获得的糖基氯被用作糖基化试剂。该反应与底物的官能团相容，并且已经以良好至优异的产率和优异的非对映选择性合成了一系列C-芳基糖苷。发现廉价的5-降冰片烯-2-腈作为瞬时介体可以有效地促进该反应。此外，IPSO -arylation和氰化还通过战略来实现。
• An efficient approach to partially O-methylated α-D-mannopyranosides using bis-tert-butyldiphenylsilyl ethers as intermediates
  作者：MaSelma Arias-Pérez、MaJesús Santos

  DOI：10.1016/0040-4020(96)00600-x

  日期：1996.8

  Differential migratory aptitudes of secondary tert-butyldiphenylsilyl (TBDPS) groups have been observed for the bis-silylated derivatives of methyl and allyl α-D-mannopyranosides under several basic media. A remarkable variation of the selectivity in the migration of the TBDPS group at position 3 (O-3 → O-2 versus O-3 → O-4) was found by changing the hardness of the base and reaction conditions. This

  在几种基本介质下，已观察到仲叔丁基二苯基甲硅烷基（TBDPS）的甲基和烯丙基α-D-甘露吡喃糖苷的双甲硅烷基化衍生物具有不同的迁移能力。通过改变碱的硬度和反应条件，发现TBDPS基团在位置3迁移的选择性有显着变化（O-3→O-2对O-3→O-4）。此行为是针对3,6-，2,6-和4,6-双-TBDPS醚3-5a，b（用于制备其他O取代的衍生物的通用中间体）的实际合成。它们成功地转化为甲基和烯丙基的2,4-，3,4-和2,3-二-O-甲基α-D-甘露吡喃糖苷（10-12a，b）。
• Highly Efficient and Practical Synthesis of 3,6-Branched Oligosaccharides
  作者：Yuguo Du、Meimei Zhang、Fanzuo Kong

  DOI：10.1021/ol000243w

  日期：2000.11.1

  [reaction: see text] A one-pot formation of the 3- and 6-OH differentially protected sugar synthon was described. A mannopyranosyl pentasaccharide and a glucopyranosyl hexasaccharide were prepared employing this new finding.

  [反应：见正文]描述了3-锅和6-OH差异保护的糖合成子的一锅形成。利用这一新发现制备了甘露吡喃糖基五糖和葡糖吡喃糖基六糖。
• Tandem Epoxidation‐Alcoholysis or Epoxidation‐Hydrolysis of Glycals Catalyzed by Titanium(IV) Isopropoxide or Venturello’s Phosphotungstate Complex
  作者：Pieter Levecque、David W. Gammon、Henok Hadgu Kinfe、Pierre Jacobs、Dirk De Vos、Bert Sels

  DOI：10.1002/adsc.200800079

  日期：2008.7.7

  Venturello’s phosphotungstate complex and titanium(IV) isopropoxide [Ti(O-i-Pr)4] were successfully used as catalysts for the epoxidation-alcoholysis of glycals using hydrogen peroxide [H2O2]. Reaction substrates included a range of variously protected glycals and different alcohols were used as solvents. Ti(O-i-Pr)4 was only effective in methanol as solvent, but gave methyl glycosides in high yields

  Venturello的磷钨酸盐络合物和异丙醇钛（IV）[Ti（O- i- Pr）4 ]已成功用作使用过氧化氢[H 2 O 2 ]的环氧乙烷缩合醇解的催化剂。反应底物包括各种受保护的糖基，不同的醇用作溶剂。钛（O- i- Pr）4仅在甲醇作为溶剂中有效，但以高收率和高选择性得到甲基糖苷。事实证明，Ventrollo复合物是一种用途广泛且高效的催化剂。除了在醇类溶剂中进行环氧化-醇解以外，它还显示了在双相条件下的活性，以允许长链醇的糖基化，并且在苄基化的葡糖的立体选择性二羟基化中非常有效。
• Regioselective Benzoylation of 6-O-Protected and 4,6-O-Diprotected Hexopyranosides as Promoted by Chiral and Achiral Ditertiary 1,2-Diamines
  作者：Guixian Hu、Andrea Vasella

  DOI：10.1002/hlca.200290018

  日期：2002.12

  Monobenzoylation of triols (6-O-silylated glycopyranosides) or diols (4,6-O-benzylidenated glycopyranosides) with benzoyl chloride and triethylamine at −60° to 23° is promoted by catalytic amounts of ditertiary 1,2-diamines. The regioselectivity depends mostly on the structure of the alcohols; it is modulated by the configuration and constitution of the diamines, as shown by comparing the effect of Oriyama's

  三醇（6- Monobenzoylation ö -silylated glycopyranosides）或二醇（4,6- ö在-60℃至23 -benzylidenated glycopyranosides）与苯甲酰氯和三乙胺°通过催化量的二叔1,2-二胺的促进。区域选择性主要取决于醇的结构。通过比较Oriyama催化剂（（S）-1和（R）-1），N，N，N ′，N′-四甲基乙二胺（TMEDA ）的作用可以看出，它受二胺的构型和组成的调节。），N，N，N'，N'-四乙基乙二胺（TEEDA），Et 3 N和EtNMe 2。催化剂的空间位阻会削弱其对反应性的影响。与在Oriyama催化剂存在下外消旋-环己烷-1,2-二醇的单和二苯甲酰基化的适度对映选择性相一致，这些二胺对区域选择性的影响相当有限。尽管与过程简单相关，但是在某些情况下，这些催化剂比单一方法可产生更高的单种苯甲酸酯收率。在制备3-