ethyl 3-O-acetyl-6-O-benzyl-2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside | 219518-10-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-O-acetyl-6-O-benzyl-2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside
• 英文别名: TrocNH(-2d)[Bn(-6)]Glc3Ac(b)-SEt；[(2S,3R,4R,5S,6R)-2-ethylsulfanyl-5-hydroxy-6-(phenylmethoxymethyl)-3-(2,2,2-trichloroethoxycarbonylamino)oxan-4-yl] acetate
• CAS: 219518-10-2
• 化学式: C₂₀H₂₆Cl₃NO₇S
• 分子量: 530.854
• InChiKey: YAODWMDVQNBVAT-ZKXLYKBJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  32
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  129
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-acetyl-6-O-benzyl-2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside 在 吡啶 、 甲磺酰溴 、 silver trifluoromethanesulfonate 、 乙二胺 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 22.58h， 生成 Acetic acid (2R,3R,4R,5R,6S)-3-acetoxy-6-[(2R,3S,4R,5R,6S)-5-amino-2-benzyloxymethyl-4-hydroxy-6-(4-methoxy-phenoxy)-tetrahydro-pyran-3-yloxy]-2-benzyloxymethyl-5-(2,2,2-trichloro-ethoxycarbonylamino)-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  Synthesis of Lactam and Acetamido Analogues of Sialyl Lewis x Tetrasaccharide and Lewis x Trisaccharide

  摘要：

  Virtually complete regioselective galactosylation of the diol acceptor p-methoxyphenyl 6-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (15) with the donors ethyl 3,4-di-O-acetyl-6-O-benzyl-2-deoxy-2-[[(2,2,2-trichloroethoxy)carbonyl]amino]-1-beta-D-galactopyranoside (14), 4-methylphenyl 2,3-di-O-acetyl-4-azido-6-O-benzyl-4-deoxy-1-thio-beta-D-galactopyranoside (30), and 4-methylphenyl 2-O-acetyl-4-azido-6-O-benzyl-4-deoxy-3-O-(methoxyethanoyl)-1-thio-beta-D-galactopyranoside (44) gave the lactose-diamine derivatives 16, 33, and 45, respectively. Fucosylation of the NHAc derivatives of 16 and 33 (17 and 34) with the donor 18 gave, after deprotection and N-acetylation, the 2-NHAc-Le(x) and 4-NKAc-Le(x) trisaccharides 3 and 5, respectively. Removal of the Troc group from the tetrasaccharide intermediate 23, followed by N-acetylation (-->24), gave the NHAc-SLe(x) tetrasaccharide 2. Regioselective sialylation of the partially protected trisaccharide diols 21 and 37 with the sialyl donors 22 and 38 gave, after deprotection and lactamization, the SLe(x)-1'''-->2-lactam 1 and the SLe(x)-1'''-->4'-lactam 4, respectively. The stannylidene acetal of the trisaccharide diol 21 was regioselectively 3-O-alkylated with tert-butyl bromoacetate; reductive removal of the Tree protecting group and addition of methanolic MeONa caused formation of a lactam ring. Compound 40 was thus obtained over four steps in an overall yield of 52%. Deprotection of 40 furnished the Le(x)-3,2-lactam 6 in 74% yield. Fucosylation of the lactose-diamine derivative 46 with donor 18 gave the N-3-Le(x) trisaccharide derivative 47. The azido function of 47 was reduced with H2S, which caused spontaneous closure of a lactam ring. Removal of the protecting groups then gave the Le(x)-3,4-lactam 7. The total yields of 1, 2, 3, 4, 5, and 7 from the monosaccharide starting materials 14, 15, 18, 22, 30, 38, and 44 were 10%, 10%, 22%, 14%, 62%, and 28%, respectively.

  DOI：

  10.1021/jo981204p
• 作为产物：
  描述：

  ethyl 2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside 在 盐酸 、 4-二甲氨基吡啶 、 3 Angstroems MS 、 sodium cyanoborohydride 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 吡啶 、 乙醚 、 乙腈 为溶剂， 反应 7.0h， 生成 ethyl 3-O-acetyl-6-O-benzyl-2-deoxy-<<(2,2,2-trichloroethoxy)carbonyl>amino>-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of Lactam and Acetamido Analogues of Sialyl Lewis x Tetrasaccharide and Lewis x Trisaccharide

  摘要：

  Virtually complete regioselective galactosylation of the diol acceptor p-methoxyphenyl 6-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (15) with the donors ethyl 3,4-di-O-acetyl-6-O-benzyl-2-deoxy-2-[[(2,2,2-trichloroethoxy)carbonyl]amino]-1-beta-D-galactopyranoside (14), 4-methylphenyl 2,3-di-O-acetyl-4-azido-6-O-benzyl-4-deoxy-1-thio-beta-D-galactopyranoside (30), and 4-methylphenyl 2-O-acetyl-4-azido-6-O-benzyl-4-deoxy-3-O-(methoxyethanoyl)-1-thio-beta-D-galactopyranoside (44) gave the lactose-diamine derivatives 16, 33, and 45, respectively. Fucosylation of the NHAc derivatives of 16 and 33 (17 and 34) with the donor 18 gave, after deprotection and N-acetylation, the 2-NHAc-Le(x) and 4-NKAc-Le(x) trisaccharides 3 and 5, respectively. Removal of the Troc group from the tetrasaccharide intermediate 23, followed by N-acetylation (-->24), gave the NHAc-SLe(x) tetrasaccharide 2. Regioselective sialylation of the partially protected trisaccharide diols 21 and 37 with the sialyl donors 22 and 38 gave, after deprotection and lactamization, the SLe(x)-1'''-->2-lactam 1 and the SLe(x)-1'''-->4'-lactam 4, respectively. The stannylidene acetal of the trisaccharide diol 21 was regioselectively 3-O-alkylated with tert-butyl bromoacetate; reductive removal of the Tree protecting group and addition of methanolic MeONa caused formation of a lactam ring. Compound 40 was thus obtained over four steps in an overall yield of 52%. Deprotection of 40 furnished the Le(x)-3,2-lactam 6 in 74% yield. Fucosylation of the lactose-diamine derivative 46 with donor 18 gave the N-3-Le(x) trisaccharide derivative 47. The azido function of 47 was reduced with H2S, which caused spontaneous closure of a lactam ring. Removal of the protecting groups then gave the Le(x)-3,4-lactam 7. The total yields of 1, 2, 3, 4, 5, and 7 from the monosaccharide starting materials 14, 15, 18, 22, 30, 38, and 44 were 10%, 10%, 22%, 14%, 62%, and 28%, respectively.

  DOI：

  10.1021/jo981204p

文献信息

• Synthesis of Deoxygenated Disaccharide Precursors for Modified Lipid II Synthesis
  作者：De-Qun Sun、Roger Busson、Piet Herdewijn

  DOI：10.1002/ejoc.200600515

  日期：2006.11

  The synthesis of novel deoxygenated disaccharide precursors for modified lipid II synthesis is described. The 3- and 4-deoxy-GlcNAc donors were obtained, respectively, by radical reduction of the iodo derivative by TBTH/AIBN and hydrogen reduction of the triflate using a borohydride reagent (nBu4NBH4). O-Glycosylation of the acceptor, promoted by NIS/TMSOTf, led to the 3- and 4-deoxygenated disaccharides

  描述了用于修饰脂质 II 合成的新型脱氧二糖前体的合成。通过 TBTH/AIBN 自由基还原碘衍生物和使用硼氢化物试剂 (nBu4NBH4) 氢还原三氟甲磺酸酯，分别获得 3-和 4-脱氧-GlcNAc 供体。NIS/TMSOTf 促进受体的 O-糖基化，产生 3-和 4-脱氧二糖。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)