4-pentenyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1->2)-3,4-carbonyl-6-O-tri-isopropylsilyl-β-D-galactopyranosyl-(1->3)-6-O-tri-isopropylsilyl-2-deoxy-2-phenylsulfonlyamino-β-D-galactopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-pentenyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1->2)-3,4-carbonyl-6-O-tri-isopropylsilyl-β-D-galactopyranosyl-(1->3)-6-O-tri-isopropylsilyl-2-deoxy-2-phenylsulfonlyamino-β-D-galactopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: N-[(2S,3R,4R,5R,6R)-4-[[(3aS,4R,6R,7R,7aS)-7-[(2S,3S,4R,5R,6S)-6-methyl-3,4,5-tris(phenylmethoxy)oxan-2-yl]oxy-2-oxo-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-5-hydroxy-2-[(2R,3R,4S,5S,6R)-2-[(2R,3S,4S,5R,6S)-6-[(2R,3R,4S,5R,6R)-6-pent-4-enoxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxy-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-yl]oxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl]benzenesulfonamide
• 化学式: C₁₅₀H₁₈₅NO₃₂SSi₂
• 分子量: 2602.34
• InChiKey: OASSOTDXSZFYGI-YOQTZPGOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  26.18
• 重原子数：
  186
• 可旋转键数：
  69
• 环数：
  20.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  350
• 氢给体数：
  2
• 氢受体数：
  33

反应信息

• 作为反应物：
  描述：

  4-pentenyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1->2)-3,4-carbonyl-6-O-tri-isopropylsilyl-β-D-galactopyranosyl-(1->3)-6-O-tri-isopropylsilyl-2-deoxy-2-phenylsulfonlyamino-β-D-galactopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside 在 sodium methylate 、 四丁基氟化铵 作用下， 以 甲醇 、 二氯甲烷 、 四氢呋喃 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  Synthesis of Human Cancer Associated Globo-H (MBr1) Glycosylamino Acid: Some Mechanistic and Conformational Reinvestigations

  摘要：

  The synthesis of an extended globo-H (MBr1 antigen) in the form of a glycosylamino acid is reported. By careful NMR analysis, we found an interesting conformational "flip" on the E ring of some synthetic intermediates. An explanation offered for the successful [3+3] coupling of ABC acceptor 11 and DEF donor 10 possessing a C4 free hydroxyl to produce beta-galactoside in azaglycosidations is reinforced.

  DOI：

  10.3987/com-08-s(d)82
• 作为产物：
  描述：

  ethyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1->2)-3,4-carbonyl-6-O-tri-isopropylsilyl-β-D-galactopyranosyl-(1->3)-6-O-tri-isopropylsilyl-2-deoxy-2-phenylsulfonlyamino-1-thio-β-D-galactopyranoside 、 4-pentenyl 2,4,6-tri-O-benzyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside 在 4 A molecular sieve 、 三氟甲烷磺酸甲酯 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 5.0h， 以60%的产率得到4-pentenyl 2,3,4-tri-O-benzyl-α-L-fucopyranosyl-(1->2)-3,4-carbonyl-6-O-tri-isopropylsilyl-β-D-galactopyranosyl-(1->3)-6-O-tri-isopropylsilyl-2-deoxy-2-phenylsulfonlyamino-β-D-galactopyranosyl-(1->3)-2,4,6-tri-O-benzyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  MBr1（globo-H）乳腺肿瘤抗原的第二代合成：正戊烯基糖苷方法在实现复杂糖蛋白连接方面的新应用。

  摘要：

  报道了六糖MBr1抗原（globo-H）的新合成。由于含有这种抗原的抗癌疫苗正进入前列腺癌的II期和III期临床试验，因此有必要对结构进行改进以提高效率。第二代合成的关键特征是制备globo-H作为其正戊烯基糖苷。该基团用作端基保护基和用作与载体蛋白生物缀合的接头。所得的合成物允许产生适当量的globo-H用于临床试验。

  DOI：

  10.1002/(sici)1521-3765(20000417)6:8<1366::aid-chem1366>3.0.co;2-k

文献信息

• A Second Generation Synthesis of the MBr1 (Globo-H) Breast Tumor Antigen: New Application of then-Pentenyl Glycoside Method for Achieving Complex Carbohydrate Protein Linkages
  作者：Jennifer R. Allen、John G. Allen、Xu-Feng Zhang、Lawrence J. Williams、Andrzej Zatorski、Govindaswami Ragupathi、Philip O. Livingston、Samuel J. Danishefsky

  DOI：10.1002/(sici)1521-3765(20000417)6:8<1366::aid-chem1366>3.0.co;2-k

  日期：2000.4.17

  A new synthesis of the hexasaccharide MBr1 antigen (globo-H) is reported. A revised construction with improved efficiency was necessary because an anti-cancer vaccine containing this antigen is entering phase II and phase III clinical trials for prostate cancer. The key feature of this second generation synthesis is the preparation of globo-H as its n-pentenyl glycoside. This group serves as an anomeric

  报道了六糖MBr1抗原（globo-H）的新合成。由于含有这种抗原的抗癌疫苗正进入前列腺癌的II期和III期临床试验，因此有必要对结构进行改进以提高效率。第二代合成的关键特征是制备globo-H作为其正戊烯基糖苷。该基团用作端基保护基和用作与载体蛋白生物缀合的接头。所得的合成物允许产生适当量的globo-H用于临床试验。
• A Practical Total Synthesis of Globo-H for Use in Anticancer Vaccines
  作者：Insik Jeon、Karthik Iyer、Samuel J. Danishefsky

  DOI：10.1021/jo901682p

  日期：2009.11.6

  An improved synthesis of the hexasaccharide MBr1 antigen (globo-H) is reported. Enhanced efficiency in the synthesis was necessary for the scale-up production of globo-H, in order to advance globo-H-based anticancer vaccines to clinical trials. The key features of the improved synthesis include preactivation-based glycosylations and a revised iodosulfonimidation/rearrangement.

  据报道，六糖 MBr1 抗原 (globo-H) 的合成得到了改进。提高合成效率对于扩大 globo-H 的生产规模至关重要，以便将基于 globo-H 的抗癌疫苗推进临床试验。改进合成的关键特征包括基于预激活的糖基化和改进的碘磺酰亚胺化/重排。
• Synthesis of Human Cancer Associated Globo-H (MBr1) Glycosylamino Acid: Some Mechanistic and Conformational Reinvestigations
  作者：Samuel J. Danishefsky、Jianglong Zhu、Qian Wan、Guangbin Yang、Ouathek Ouerfelli

  DOI：10.3987/com-08-s(d)82

  日期：——

  The synthesis of an extended globo-H (MBr1 antigen) in the form of a glycosylamino acid is reported. By careful NMR analysis, we found an interesting conformational "flip" on the E ring of some synthetic intermediates. An explanation offered for the successful [3+3] coupling of ABC acceptor 11 and DEF donor 10 possessing a C4 free hydroxyl to produce beta-galactoside in azaglycosidations is reinforced.