(2R)-tert-butyl 2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-3-(3'-(2'',3'',4'',6''-tetra-O-acetyl-β-D-glucopyranosyl)-oxyprop-1-enylthio)propanoate | 1261138-90-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2R)-tert-butyl 2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-3-(3'-(2'',3'',4'',6''-tetra-O-acetyl-β-D-glucopyranosyl)-oxyprop-1-enylthio)propanoate
• CAS: 1261138-90-2
• 化学式: C₃₉H₄₇NO₁₄S
• 分子量: 785.866
• InChiKey: GMIIJGBMBKYHJR-XEHBOBCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.58
• 重原子数：
  55.0
• 可旋转键数：
  15.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.49
• 拓扑面积：
  188.29
• 氢给体数：
  1.0
• 氢受体数：
  15.0

反应信息

• 作为反应物：
  描述：

  (2R)-tert-butyl 2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-3-(3'-(2'',3'',4'',6''-tetra-O-acetyl-β-D-glucopyranosyl)-oxyprop-1-enylthio)propanoate 、 N-[(tert-butoxy)carbonyl]-L-cysteine methyl ester 在 安息香双甲醚 作用下， 以 水 、 甲苯 为溶剂， 反应 2.0h， 以75%的产率得到(2R,2'RS,2''R)-methyl 2-((tert-butoxycarbonylamino)-3-(1'-(2''-((9H-fluoren-9-yl)methoxy)carbonylamino)-3''-tert-butoxy-3''-oxopropylthio)-3'-(2''',3''',4''',6'''-tetra-O-acetyl-β-D-glucopyranosyl)oxypropan-2'-ylthio)propanoate
  参考文献：
  名称：

  An Insight into the Radical Thiol/Yne Coupling: The Emergence of Arylalkyne-Tagged Sugars for the Direct Photoinduced Glycosylation of Cysteine-Containing Peptides

  摘要：

  An explorative study of the Thiol-Yne Coupling (TYC) reaction has been carried out using an aliphatic (1-octyne) and an aromatic alkyne (phenylacetylene) and two alkanethiols (methyl thioglycolate and N-acetyl-L-cysteine methyl ester). The outcomes of the TYC reactions strongly depend on the experimental conditions (e.g., temperature, solvent, and alkyne/thiol ratio), but these can be properly adjusted to achieve selective production of either mono- or bis-coupling products. With respect to 1-octyne, phenylacetylene undergoes notably easier radical hydrothiolation, further showing a notably higher aptitude for monohydrothiolation exclusive of bis-hydrothiolation. The overall findings were exploited in glycosylation of cysteine derivatives as well as of cysteine-containing peptides. A sugar featuring an arylacetylene moiety gave rise to a true click-reaction, that is, glycosylation of the tripeptide glutathione in its native form, by means of virtually equimolar amounts of reagents. This reaction was successfully applied, under physiological conditions, to a cysteine-containing nonapeptide with marked advantages over the analogous Thiol-Ene Coupling (TEC) derivatization. A TYC/TEC sequence affording bis-armed cysteine derivatives through dual functionalization of an alkynyl sugar was additionally devised.

  DOI：

  10.1021/jo101906j