4,5,6,8-tetra-O-benzyl-1,1,2,2-tetradehydro-1,2-dideoxy-1-C-(trimethylsilyl)-D-mannooct-3-ulopyranose | 887644-42-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,5,6,8-tetra-O-benzyl-1,1,2,2-tetradehydro-1,2-dideoxy-1-C-(trimethylsilyl)-D-mannooct-3-ulopyranose
• 英文别名: 1-trimethylsilylethynyl-2,3,4,6-tetra-O-benzyl-D-mannopyranose；(3S,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)-2-(2-trimethylsilylethynyl)oxan-2-ol
• CAS: 887644-42-0
• 化学式: C₃₉H₄₄O₆Si
• 分子量: 636.86
• InChiKey: REUVVWZCBGEXSE-ZEFPQDMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.93
• 重原子数：
  46
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4,5,6,8-tetra-O-benzyl-1,1,2,2-tetradehydro-1,2-dideoxy-1-C-(trimethylsilyl)-D-mannooct-3-ulopyranose 在 三乙基硅烷 、 三氟化硼乙醚 、 四丁基氟化铵 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 (2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)ethyne
  参考文献：
  名称：

  Synthesis of β-analogues of C-mannosyltryptophan, a novel C-glycosylamino acid found in proteins

  摘要：

  α-C-甘露糖基色氨酸（α-C-Man-Trp）被发现是一种新的色氨酸翻译后修饰，存在于一些生物重要的糖蛋白中。为了分析α-C-Man-Trp的生物功能，我们开发了一种高效的合成策略，用于α-C-Man-Trp及其葡萄糖和半乳糖类似物，从对应的六糖派拉诺糖衍生物与乙炔锡的α-C-糖苷化反应开始。根据合成路线，我们在此描述了从相应的β-C-糖苷乙炔衍生物合成β-异构体的C-Man-Trp及其葡萄糖和半乳糖类似物。在这项研究中，我们开发了一种高度立体选择性合成β-C-甘露糖基乙炔的方法，这是合成β-C-Man-Trp所必需的，而先前的方法则给出了C-甘露糖基乙炔的异构体混合物。合成的C-Man-Trp及其类似物通过高效液相色谱（HPLC）进行了分析。

  DOI：

  10.1039/b516282c
• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzyl-D-mannopyranose 在 正丁基锂 、 乙酸酐 作用下， 以 四氢呋喃 、 正己烷 、 二甲基亚砜 为溶剂， 反应 10.5h， 生成 4,5,6,8-tetra-O-benzyl-1,1,2,2-tetradehydro-1,2-dideoxy-1-C-(trimethylsilyl)-D-mannooct-3-ulopyranose
  参考文献：
  名称：

  Synthesis of β-analogues of C-mannosyltryptophan, a novel C-glycosylamino acid found in proteins

  摘要：

  α-C-甘露糖基色氨酸（α-C-Man-Trp）被发现是一种新的色氨酸翻译后修饰，存在于一些生物重要的糖蛋白中。为了分析α-C-Man-Trp的生物功能，我们开发了一种高效的合成策略，用于α-C-Man-Trp及其葡萄糖和半乳糖类似物，从对应的六糖派拉诺糖衍生物与乙炔锡的α-C-糖苷化反应开始。根据合成路线，我们在此描述了从相应的β-C-糖苷乙炔衍生物合成β-异构体的C-Man-Trp及其葡萄糖和半乳糖类似物。在这项研究中，我们开发了一种高度立体选择性合成β-C-甘露糖基乙炔的方法，这是合成β-C-Man-Trp所必需的，而先前的方法则给出了C-甘露糖基乙炔的异构体混合物。合成的C-Man-Trp及其类似物通过高效液相色谱（HPLC）进行了分析。

  DOI：

  10.1039/b516282c

文献信息

• Novel Type of Rigid C-Linked Glycosylacetylene−Phenylalanine Building Blocks for Combinatorial Synthesis of C-linked Glycopeptides
  作者：Todd Lowary、Morten Meldal、Arnim Helmboldt、Andrea Vasella、Klaus Bock

  DOI：10.1021/jo980517h

  日期：1998.12.1

  C-linked 3- and 4-(glycosylacetylene)-Fmoc-phenylalanines were synthesized as rigid building blocks for synthesis of libraries of neoglycopeptide templates. Perbenzylated 1,5-galactonolactone, 1,5-gluconolactone, and 1,5-mannonolactone were reacted with cerium TMS-acetylide and the products reduced to the C-glycosylacetylene-TMS derivatives. The gluco and galacto configurations yielded exclusively the beta-C-glycoside, whereas the mannonolactone gave a mixture of alpha-C- and beta-C-anomer. The products were subjected to acetolysis and TMS cleavage. The resulting peracetylated glycosylacetylenes were cross-coupled with the (R,S)-N-alpha-acetyl-3- and 4-iodophenylalanine O-methyl esters by Pd(0) catalysis in piperidine to give the eight possible C-linked glycosyl amino acid building blocks 33-40 as diastereomeric pairs. These were O-deacetylated. As an example of further conversion into neoglycopeptide templates the N-acetyl group of the 4-linked galacto-diastereomeric pair 43 was hydrolyzed selectively by acylase 1 and separated from the (R)stereoisomer. The product was converted to 4-(beta-C-galactosylacetylene)(N-alpha-Fmoc-)-L-phenylalanine (52) by reaction with Fmoc-OSu. Acid hydrolysis of galactosyl acetylene phenyl alanine 43 at elevated temperature afforded the conversion of the acetylene to the 1'-oxo derivative which was also N-alpha-Fmoc protected. The building blocks were used in the glycopeptide synthesis of three neoglycopeptide templates 54, 55, and 56 known to bind to murine MHC class II E-k and to present the glycan for interaction with the T-cell receptor. This template has previously been employed to elicit a carbohydrate specific T-cell response.
• Synthesis of β-analogues of C-mannosyltryptophan, a novel C-glycosylamino acid found in proteins
  作者：Toshio Nishikawa、Yuya Koide、Akira Kanakubo、Hiroshi Yoshimura、Minoru Isobe

  DOI：10.1039/b516282c

  日期：——

  α-C-Mannosyltryptophan (α-C-Man-Trp) has been found to be a novel post-translational modification of tryptophan found from some biologically important glycoproteins. In order to analyze the biological functions of α-C-Man-Trp, we have developed an efficient synthetic strategy for α-C-Man-Trp and its glucose and galactose analogues, starting from α-C-glycosidation of the corresponding hexapyranoside derivatives with tinacetylene. According to the synthetic routes, we describe here syntheses of β-anomers of C-Man-Trp, and its glucose and galactose analogues from the corresponding β-C-glycosylacetylenes. During this study, we have developed a highly stereocontrolled synthesis of β-C-mannosylacetylene that is required for the synthesis of β-C-Man-Trp, while the precedented method gave an anomeric mixture of the C-mannosylacetylene. The synthetic C-Man-Trp and its analogues were analyzed by HPLC.

  α-C-甘露糖基色氨酸（α-C-Man-Trp）被发现是一种新的色氨酸翻译后修饰，存在于一些生物重要的糖蛋白中。为了分析α-C-Man-Trp的生物功能，我们开发了一种高效的合成策略，用于α-C-Man-Trp及其葡萄糖和半乳糖类似物，从对应的六糖派拉诺糖衍生物与乙炔锡的α-C-糖苷化反应开始。根据合成路线，我们在此描述了从相应的β-C-糖苷乙炔衍生物合成β-异构体的C-Man-Trp及其葡萄糖和半乳糖类似物。在这项研究中，我们开发了一种高度立体选择性合成β-C-甘露糖基乙炔的方法，这是合成β-C-Man-Trp所必需的，而先前的方法则给出了C-甘露糖基乙炔的异构体混合物。合成的C-Man-Trp及其类似物通过高效液相色谱（HPLC）进行了分析。