(3aS,5R,6S,7S,7aS)-5-(tert-Butyl-diphenyl-silanyloxymethyl)-2-pent-4-enyloxy-2-phenyl-tetrahydro-[1,3]dioxolo[4,5-b]pyran-6,7-diol | 870101-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (3aS,5R,6S,7S,7aS)-5-(tert-Butyl-diphenyl-silanyloxymethyl)-2-pent-4-enyloxy-2-phenyl-tetrahydro-[1,3]dioxolo[4,5-b]pyran-6,7-diol
• 英文别名: (3aS,5R,6S,7S,7aS)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-2-pent-4-enoxy-2-phenyl-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-6,7-diol
• CAS: 870101-07-8
• 化学式: C₃₄H₄₂O₇Si
• 分子量: 590.789
• InChiKey: DPSUPWBAGIBHCD-OXRLVDJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  42
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  86.6
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (3aS,5R,6S,7S,7aS)-5-(tert-Butyl-diphenyl-silanyloxymethyl)-2-pent-4-enyloxy-2-phenyl-tetrahydro-[1,3]dioxolo[4,5-b]pyran-6,7-diol 在 N-溴代丁二酰亚胺(NBS) 、 三氟化硼乙醚 、 sodium methylate 作用下， 生成 Bz(-2)[Bz(-3)][Bz(-4)][Bz(-6)]Man(a1-3)[TBDPS(-6)]Man(a1-6)a-Glc1Me2Me3Me4Me
  参考文献：
  名称：

  基于多元醇受体与部分未保护的正戊烯基-原酸酯的区域选择性糖基化的寡糖合成的迭代正交策略：相互供体受体选择性（RDAS）的进一步证据。

  摘要：

  基于D-甘露糖多元醇与部分未保护的正戊烯基原酸酯供体的区域选择性糖基偶联的有效的迭代正交方案允许合成具有最小保护基篡改的直链和支链寡糖。

  DOI：

  10.1039/b507468a
• 作为产物：
  描述：

  (3aS,5R,6S,7S,7aS)-5-(hydroxymethyl)-2-pent-4-enoxy-2-phenyl-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-6,7-diol 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以16.56 g的产率得到(3aS,5R,6S,7S,7aS)-5-(tert-Butyl-diphenyl-silanyloxymethyl)-2-pent-4-enyloxy-2-phenyl-tetrahydro-[1,3]dioxolo[4,5-b]pyran-6,7-diol
  参考文献：
  名称：

  Studies Related to Synthesis of Glycophosphatidylinositol Membrane-Bound Protein Anchors. 5. n-Pentenyl Ortho Esters for Mannan Components

  摘要：

  Procedures for rapid assembly of multigram amounts of mannan components have been examined. Although these studies are reported in the context of the mannan moiety of the glycan anchors of membrane-bound glycoproteins, the procedures should be applicable to the wider family of mannose-containing glycoproteins. Readily prepared n-pentenyl ortho esters of mannose are shown to be versatile substrates that can serve as glycosyl donors in their own right or be used to furnish mannosyl bromides or n-pentenyl alpha-D-mannosides. Thus three glycosyl donors of different reactivities and stabilities are obtainable from the same precursor, all three being activated under mild conditions. Two approaches are described. in the first, a portion of the starting n-pentenyl ortho ester is converted into an n-pentenyl glycoside (NPG) by acid-catalyzed rearrangement, while another portion is titrated with bromine to give a glycosyl bromide. These are coupled under Koenigs-Knorr conditions to give an n-pentenyl disaccharide which is then processed to become a glycosyl acceptor. A third portion of the ortho ester, after suitable protecting group adjustments, is also titrated with bromine and coupled to the disaccharide acceptor to give the desired trimannan. The instability of glycosyl bromides detracts from this route, and so a second approach which avoids their use completely was pursued in which NPG obtained from the acid-catalyzed rearrangement was converted into a vicinal dibromide. The latter is then able to serve as a glycosyl acceptor for coupling to a donor obtainable by reaction of the n-pentenyl ortho ester with halonium ion. The dibromopentanyl disaccharide produced then becomes an acceptor for a donor derived from n-pentenyl mannoside. The second approach uses no unstable reactants, is therefore experimentally less demanding, and can be operated conveniently on a large scale.

  DOI：

  10.1021/ja00110a010

文献信息

• Reaction of 1,2-Orthoesters with HF−Pyridine: A Method for the Preparation of Partly Unprotected Glycosyl Fluorides and Their Use in Saccharide Synthesis
  作者：J. Cristóbal López、Juan Ventura、Clara Uriel、Ana M. Gómez、Bert Fraser-Reid

  DOI：10.1021/ol901630d

  日期：2009.9.17

  Glycosyl fluorides can be prepared In an efficient manner by treatment of pyranose- or furanose-derived 1,2-orthoesters, with hydrogen fluoride pyridine (HF-py). The method is compatible with the presence of a variety of protecting groups, including tert-butyldiphenyl silyl ethers, and can be applied to sugar derivatives with free hydroxyl groups, thus avoiding the need for the protection-deprotection steps.
• Iterative, orthogonal strategy for oligosaccharide synthesis based on the regioselective glycosylation of polyol acceptors with partially unprotected n-pentenyl-orthoesters: further evidence for reciprocal donor acceptor selectivity (RDAS)
  作者：J. Cristóbal López、Attila Agocs、Clara Uriel、Ana M. Gómez、Bert Fraser-Reid

  DOI：10.1039/b507468a

  日期：——

  An efficient iterative, orthogonal protocol based on the regioselective glycosyl coupling of D-mannose polyols with, partially unprotected, n-pentenyl orthoester donors permits the synthesis of linear and branched oligosaccharides with minimal protecting group tampering.

  基于D-甘露糖多元醇与部分未保护的正戊烯基原酸酯供体的区域选择性糖基偶联的有效的迭代正交方案允许合成具有最小保护基篡改的直链和支链寡糖。
• Studies Related to Synthesis of Glycophosphatidylinositol Membrane-Bound Protein Anchors. 5. n-Pentenyl Ortho Esters for Mannan Components
  作者：Carmichael Roberts、Robert Madsen、Bert Fraser-Reid

  DOI：10.1021/ja00110a010

  日期：1995.2

  Procedures for rapid assembly of multigram amounts of mannan components have been examined. Although these studies are reported in the context of the mannan moiety of the glycan anchors of membrane-bound glycoproteins, the procedures should be applicable to the wider family of mannose-containing glycoproteins. Readily prepared n-pentenyl ortho esters of mannose are shown to be versatile substrates that can serve as glycosyl donors in their own right or be used to furnish mannosyl bromides or n-pentenyl alpha-D-mannosides. Thus three glycosyl donors of different reactivities and stabilities are obtainable from the same precursor, all three being activated under mild conditions. Two approaches are described. in the first, a portion of the starting n-pentenyl ortho ester is converted into an n-pentenyl glycoside (NPG) by acid-catalyzed rearrangement, while another portion is titrated with bromine to give a glycosyl bromide. These are coupled under Koenigs-Knorr conditions to give an n-pentenyl disaccharide which is then processed to become a glycosyl acceptor. A third portion of the ortho ester, after suitable protecting group adjustments, is also titrated with bromine and coupled to the disaccharide acceptor to give the desired trimannan. The instability of glycosyl bromides detracts from this route, and so a second approach which avoids their use completely was pursued in which NPG obtained from the acid-catalyzed rearrangement was converted into a vicinal dibromide. The latter is then able to serve as a glycosyl acceptor for coupling to a donor obtainable by reaction of the n-pentenyl ortho ester with halonium ion. The dibromopentanyl disaccharide produced then becomes an acceptor for a donor derived from n-pentenyl mannoside. The second approach uses no unstable reactants, is therefore experimentally less demanding, and can be operated conveniently on a large scale.