[(4aR,6S,7R,8R,8aR)-2,2-ditert-butyl-6-phenylsulfanyl-7-(2,2,2-trichloroethoxycarbonylamino)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3,2]dioxasilin-8-yl] acetate | 612844-13-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: [(4aR,6S,7R,8R,8aR)-2,2-ditert-butyl-6-phenylsulfanyl-7-(2,2,2-trichloroethoxycarbonylamino)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3,2]dioxasilin-8-yl] acetate
• CAS: 612844-13-0
• 化学式: C₂₅H₃₆Cl₃NO₇SSi
• 分子量: 629.074
• InChiKey: HIXARQLVSCUYDH-ADAARDCZSA-N

物化性质

• 沸点：
  632.7±55.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.36
• 重原子数：
  38
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  118
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [(4aR,6S,7R,8R,8aR)-2,2-ditert-butyl-6-phenylsulfanyl-7-(2,2,2-trichloroethoxycarbonylamino)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3,2]dioxasilin-8-yl] acetate 在 N-溴代丁二酰亚胺(NBS) 、 二乙胺基三氟化硫 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 p-nitrophenyl 3-O-acteyl-2-deoxy-4,6-O-di-tert-butylsilylene-2-(2,2,2-trichloroethoxycarbamoyl)-α-D-galactopyranoside
  参考文献：
  名称：

  与C2参与基团相容的二叔丁基亚甲硅烷基定向的α-占优势的半乳糖基化在各种糖苷组装方面的扩展应用。

  摘要：

  二叔丁基亚甲硅烷基（DTBS）指导的α占主导地位的半乳糖基化的高通用性已扩展到困难的聚糖序列的构建。首先，为研究α-优势反应与各种糖基化系统的相容性，有效合成了各种4,6-O-DTBS系链的半乳糖胺基或半乳糖基供体，这些供体具有C2参与基团，具有多个离去基团，例如作为烷基亚磺酰基，卤化物，三氯乙酰亚胺基。使用糖基供体的糖基化反应的详细检查结果表明，由4,6-DTBS定向的α-半乳糖基化范围很广。在下一步中，通过采用DTBS定向的糖基化来检查alpha-GalN-Ser / Thr序列的立体选择性构建。因此，各种类型的丝氨酸和苏氨酸衍生物被糖基化，进行了高选择性的α-GalN-Ser/ Thr序列糖基化。此外，DTBS定向的半乳糖基化已成功地用于糖蛋白A的α-四糖基-Ser片段的合成。

  DOI：

  10.1002/chem.200600832
• 作为产物：
  描述：

  phenyl 2-deoxy-1-thio-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-galactopyranoside 以 吡啶 为溶剂， 反应 0.22h， 生成 [(4aR,6S,7R,8R,8aR)-2,2-ditert-butyl-6-phenylsulfanyl-7-(2,2,2-trichloroethoxycarbonylamino)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3,2]dioxasilin-8-yl] acetate
  参考文献：
  名称：

  与C2参与基团相容的二叔丁基亚甲硅烷基定向的α-占优势的半乳糖基化在各种糖苷组装方面的扩展应用。

  摘要：

  二叔丁基亚甲硅烷基（DTBS）指导的α占主导地位的半乳糖基化的高通用性已扩展到困难的聚糖序列的构建。首先，为研究α-优势反应与各种糖基化系统的相容性，有效合成了各种4,6-O-DTBS系链的半乳糖胺基或半乳糖基供体，这些供体具有C2参与基团，具有多个离去基团，例如作为烷基亚磺酰基，卤化物，三氯乙酰亚胺基。使用糖基供体的糖基化反应的详细检查结果表明，由4,6-DTBS定向的α-半乳糖基化范围很广。在下一步中，通过采用DTBS定向的糖基化来检查alpha-GalN-Ser / Thr序列的立体选择性构建。因此，各种类型的丝氨酸和苏氨酸衍生物被糖基化，进行了高选择性的α-GalN-Ser/ Thr序列糖基化。此外，DTBS定向的半乳糖基化已成功地用于糖蛋白A的α-四糖基-Ser片段的合成。

  DOI：

  10.1002/chem.200600832

文献信息

• Endolysins of <i>Bacillus anthracis</i> Bacteriophages Recognize Unique Carbohydrate Epitopes of Vegetative Cell Wall Polysaccharides with High Affinity and Selectivity
  作者：Kai-For Mo、Xiuru Li、Huiqing Li、Lieh Yoon Low、Conrad P. Quinn、Geert-Jan Boons

  DOI：10.1021/ja3069962

  日期：2012.9.19

  Bacteriophages express endolysins which are the enzymes that hydrolyze peptidoglycan resulting in cell lysis and release of bacteriophages. Endolysins have acquired stringent substrate specificities, which have been attributed to cell wall binding domains (CBD). Although it has been realized that CBDs of bacteriophages that infect Gram-positive bacteria target cell wall carbohydrate structures, molecular

  噬菌体表达内溶素，内溶素是水解肽聚糖的酶，导致细胞裂解并释放噬菌体。内溶素具有严格的底物特异性，这归因于细胞壁结合域（CBD）。尽管人们已经认识到感染革兰氏阳性菌的噬菌体的 CBD 以细胞壁碳水化合物结构为目标，但赋予选择性的分子机制尚不清楚。一系列源自炭疽芽孢杆菌次生细胞壁多糖的寡糖已被化学合成。该化合物含有 α-d-GlcNAc-(1→4)-β-d-ManNAc-(1→4)-β-d-GlcNAc 主链，该主链由各种 α-d-Gal 和 β-d 模式修饰-Gal分支点。通过使用由正交保护基团 N(α)-9-芴基甲氧基碳酸酯 (Fmoc)、2-甲基萘基醚 (Nap)、乙酰丙酰酯 (Lev) 和二甲基己基甲硅烷基醚 (TDS) 修饰的核心三糖，可以轻松制备化合物库在关键的分支点。通过表面等离振子共振 (SPR) 测定细胞内溶素 PlyL 和 PlyG 的细胞壁结合域的解离常数。发现半乳糖基化
• Synthesis of the 3’-<i>O</i>-sulfated TF antigen with a TEG-N₃ linker for glycodendrimersomes preparation to study lectin binding
  作者：Mark Reihill、Hanyue Ma、Dennis Bengtsson、Stefan Oscarson

  DOI：10.3762/bjoc.20.17

  日期：——

  Abstract The synthesis of gram quantities of the TF antigen (β-ᴅ-Gal-(1→3)-α-ᴅ-GalNAc) and its 3’-sulfated analogue with a TEG-N3 spacer attached is described. The synthesis of the TF antigen comprises seven steps, from a known N-Troc-protected galactosamine donor, with an overall yield of 31%. Both the spacer (85%) and the galactose moiety (79%) were introduced using thioglycoside donors in NIS/AgOTf-promoted

  抽象的 描述了克量的 TF 抗原 (β-ᴅ-Gal-(1→3)-α-ᴅ-GalNAc) 及其带有 TEG-N 3间隔基的 3'-硫酸化类似物的合成。 TF抗原的合成包括七个步骤，来自已知的N -Troc保护的半乳糖胺供体，总产率为31%。在 NIS/AgOTf 促进的糖基化反应中，使用硫代糖苷供体引入间隔基 (85%) 和半乳糖部分 (79%)。最终通过苯/DMF 中的锡活化引入 3'-硫酸盐，然后用三氧化硫-三甲胺络合物处理，产率 66%。 Beilstein J. Org. Chem. 2024, 20, 173–180. doi:10.3762/bjoc.20.17
• Chemical Synthesis and Immunological Evaluation of the Inner Core Oligosaccharide of Francisella tularensis
  作者：Thomas J. Boltje、Wei Zhong、Jin Park、Margreet A. Wolfert、Wangxue Chen、Geert-Jan Boons

  DOI：10.1021/ja306274v

  日期：2012.8.29

  Francisella tularensis, which is a Gram negative bacterium that causes tularemia, has been classified by the Center for Disease Control and Prevention (CDC) as a category A bioweapon. The development of vaccines, immunotherapeutics, and diagnostics for F. tularensis requires a detailed knowledge of the saccharide structures that can be recognized by protective antibodies. We have synthesized the inner core region of the lipopolysaccharide (LPS) of F. tularensis to probe antigenic responses elicited by a live and subunit vaccine. The successful preparation of the target compound relied on the use of a disaccharide which was modified by the orthogonal protecting groups diethylisopropylsilyl (DEIPS), 2-naphthylmethyl (Nap), allyl ether (All), and levulinoyl (Lev) ester. The ability to remove the protecting groups in different orders made it possible to establish the optimal glycosylations sequence to prepare a highly crowded 1,2,3-cis configured branching point. A variety of different methods were exploited to control anomeric selectivities of the glycosylations. A comparison of the H-1 NMR spectra of isolated material and the synthetic derivative confirmed the reported structural assignment of the inner core oligosaccharide of F. tularensis. The observation that immunizations with LPS lead to antibody responses to the inner core saccharides provides an impetus to further explore this compound as a vaccine candidate.
• Di-tert-butylsilylene (DTBS) group-directed α-selective galactosylation unaffected by C-2 participating functionalities
  作者：Akihiro Imamura、Hiromune Ando、Satomi Korogi、Genzoh Tanabe、Osamu Muraoka、Hideharu Ishida、Makoto Kiso

  DOI：10.1016/s0040-4039(03)01647-2

  日期：2003.8

  We have discovered an unusual alpha-galactosylation using phenylthioglycoside of 4,6-O-di-tert-butylsilylene (DTBS)-protected galactose derivatives as a glycosyl donor, which was not hampered by the neighboring participation of C-2 acyl functionality such as NTroc and OBz. The power of the DTBS effect has been exemplified by the coupling reaction with various glycosyl acceptors. (C) 2003 Elsevier Ltd. All rights reserved.
• METHOD OF ALPHA-SELECTIVE GLYCOSYLATION
  申请人：Japan Science and Technology Agency

  公开号：EP1626053B1

  公开（公告）日：2011-07-06