benzylN-(((9H-fluoren-9-yl)methoxy)carbonyl)-O-((3aR,4R,6S,7R,7aR)-7-azido-2,2-dimethyl-4-(((triisopropylsilyl)oxy)methyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-yl)-L-serinate | 213331-74-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: benzylN-(((9H-fluoren-9-yl)methoxy)carbonyl)-O-((3aR,4R,6S,7R,7aR)-7-azido-2,2-dimethyl-4-(((triisopropylsilyl)oxy)methyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-yl)-L-serinate
• CAS: 213331-74-9
• 化学式: C₄₃H₅₆N₄O₉Si
• 分子量: 801.025
• InChiKey: PPKCYMFJOMTCKN-VOZQLZCDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.77
• 重原子数：
  57.0
• 可旋转键数：
  16.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  159.54
• 氢给体数：
  1.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  benzylN-(((9H-fluoren-9-yl)methoxy)carbonyl)-O-((3aR,4R,6S,7R,7aR)-7-azido-2,2-dimethyl-4-(((triisopropylsilyl)oxy)methyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-yl)-L-serinate 在 palladium on activated charcoal 吡啶 、 甲醇 、 4-二甲氨基吡啶 、 TEA 、 氢气 、 碘 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 90.0h， 生成 N-芴甲氧羰基-O-BETA-(2-乙酰氨基-2-脱氧-3,4,6-三-O-乙酰基-ALPHA-D-吡喃半乳糖基)-L-丝氨酸
  参考文献：
  名称：

  Synthetic and Immunological Studies on Clustered Modes of Mucin-Related Tn and TF O-Linked Antigens:  The Preparation of a Glycopeptide-Based Vaccine for Clinical Trials against Prostate Cancer

  摘要：

  The syntheses of two tumor-associated carbohydrate antigens, Tn and TF, have been achieved using glycal assembly and cassette methodologies. These synthetic antigens were subsequently clustered (c) and immunoconjugated to a carrier protein (KLH or BSA) or a synthetic lipopeptide (pam) for immunological study. Three Tn conjugates were used to vaccinate groups of mice, and all preparations proved to be immunogenic. The Tn(c) covalently linked to KLH (27-KLH) plus the adjuvant QS-21 was the optimal vaccine, inducing high median IgM and IgG titers against Tn(c) by ELISA. These antibodies were strongly reactive with the Tn(c) positive human colon cancer cell line LS-C but not the Tn(c) negative colon cancer cell Line LS-B by FAGS. The antibodies' reactivities with natural antigens were inhibited with synthetic Tn(c) but not with structurally unrelated compounds. On the basis of these results, vaccines containing 27-KLH and 30-pam plus QS-21 are being tested in patients with prostate cancer.

  DOI：

  10.1021/ja9825128
• 作为产物：
  描述：

  (3aR,4R,7R,7aR)-7-azido-2,2-dimethyl-4-(((triisopropylsilyl)oxy) methyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-ol 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 potassium carbonate 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 8.5h， 生成 benzylN-(((9H-fluoren-9-yl)methoxy)carbonyl)-O-((3aR,4R,6S,7R,7aR)-7-azido-2,2-dimethyl-4-(((triisopropylsilyl)oxy)methyl)tetrahydro-4H-[1,3]dioxolo[4,5-c]pyran-6-yl)-L-serinate
  参考文献：
  名称：

  探索通过糖基组装构建 α-O 连接系统的方式：粘蛋白相关 F1α 抗原的全合成

  摘要：

  F1α 抗原是肿瘤相关 O 联粘蛋白糖肽的一个成员，其全合成是通过两种替代途径实现的。在第一种方法中，首先形成丝氨酸/苏氨酸和 GalNAc（2-脱氧-2-N-乙酰氨基-d-半乳糖）之间的 α-O-连接。然后将该预制盒连接到乳糖胺单元。或者，三糖糖基的组装先于糖基双键的活化和糖肽键的构建。两种策略都产生所需的糖基氨基酸衍生物。在我们的调查过程中，我们发现即使是远程保护基团对糖苷化的反应性和立体选择性也有显着影响。

  DOI：

  10.1021/ja980724z

文献信息

• Hydroxynorleucine as a glycosyl acceptor is an efficient means for introducing amino acid functionality into complex carbohydrates
  作者：Stacy J. Keding、Endo Atsushi、Kaustav Biswas、Andrzej Zatorski、Don M. Coltart、Samuel J. Danishefsky

  DOI：10.1016/s0040-4039(03)00517-3

  日期：2003.4

  A new approach to the synthesis of biologically relevant glycosyl amino acids using a non-natural amino acid as the glycosyl acceptor is described. The procedure involves a glycosylation reaction of a suitable carbohydrate donor with Fmoc-L-hydroxynorleucine benzyl ester. This reaction results in the direct incorporation of the amino acid moiety. The acceptor can be used for the preparation of alpha- or beta-O-linked glycosides depending upon the nature of the glycosyl donor. This method has been applied in the synthesis of six different tumor-associated carbohydrate antigens. (C) 2003 Elsevier Science Ltd. All rights reserved.