3-O-carbamoyl-4,6-O-di-tert-butylsilylene-D-glucal | 855270-66-5

• 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: 3-O-carbamoyl-4,6-O-di-tert-butylsilylene-D-glucal
• 英文别名: 3-O-carbamoyl-4,6-di-O-tert-butylsilylene-D-glucal；D-glucal carbamate；4,6-O-(di-tert-butylsilylene)-3-O-carbamoyl-D-glucal；[(4aR,8R,8aS)-2,2-ditert-butyl-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3,2]dioxasilin-8-yl] carbamate
• CAS: 855270-66-5
• 化学式: C₁₅H₂₇NO₅Si
• 分子量: 329.469
• InChiKey: AFJRKLWBFRCMJL-UTUOFQBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.82
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  80
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-O-carbamoyl-4,6-O-di-tert-butylsilylene-D-glucal 在 三乙胺 、 三氟乙酸酐 作用下， 以 四氢呋喃 为溶剂， 反应 0.58h， 生成
  参考文献：
  名称：

  乙二醇中的氰酸氰酸酯/异氰酸酯烯丙基重排：1-氨基和二氨基糖衍生物的立体选择性合成

  摘要：

  在O-，N-和C-亲核试剂的存在下，糖的[3,3]-σ烯丙基异氰酸酯/异氰酸酯重排可提供高收率的β- N-葡萄糖基和半乳糖基氨基甲酸酯，脲和酰胺。通过二羟基化将不饱和产物精制为N-糖苷，通过束缚的氨基羟基化将不饱和产物精制为1,3-二氨基糖，或通过σ重排的迭代而精制为1,2-二氨基糖。这种不含金属的方法代表了一种立体选择性合成N-糖苷和二氨基糖且完全传递立体化学信息的极好的通用方法。

  DOI：

  10.1021/acs.orglett.0c03438
• 作为产物：
  描述：

  4,6-O-di(tert-butyl)silanediyl-D-glucal 在 吡啶 、 dirhodium tetraacetate 、 盐酸羟胺 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 83.0h， 生成 3-O-carbamoyl-4,6-O-di-tert-butylsilylene-D-glucal
  参考文献：
  名称：

  Dihydropyranone Formation by Ipso C−H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid

  摘要：

  By using (N-tosyloxy)-3-O-carbamoyl-o-glucal 10, which removes the :need for a hypervalentsiodine (III) oxidant, we provide evidence for rhodium nitrenoid-mediated ipso C-H activation as the origin of a C3oxidized dihydropyranone product 3. This system may be especially susceptible to such a pathway because of the ease of forming a cation upon hydride transfer to the rhodium-complexed acyl nitrene.

  DOI：

  10.1021/jo101599q

文献信息

• Stereospecific Access to α‐ and β‐ <i>N</i> ‐Glycosylamine Derivatives by a Metal Free <i>O</i> ‐to‐ <i>N</i> [3,3]‐Sigmatropic Rearrangement
  作者：Debora Pratesi、Stefania Mirabella、Giulia Petrucci、Camilla Matassini、Cristina Faggi、Francesca Cardona、Andrea Goti

  DOI：10.1002/ejoc.202200804

  日期：2022.10.13

  C-3 with a carbamate group undergo, upon dehydration, a prompt allyl cyanate to isocyanate rearrangement to the isomeric N-glycosyl isocyanates, which give N-glycosyl carbamates and ureas by one-pot addition of alcohols or amines. The rearrangement occurs with complete stereoselectivity via a [3,3]-sigmatropic mechanism, affording α- or β-linked amines depending on the configuration at C-3 of the carbohydrate

  在 C-3 处被氨基甲酸酯基团取代的糖醇在脱水后会迅速发生氰酸烯丙酯到异氰酸酯重排，形成异构的N-糖基异氰酸酯，通过一锅法添加醇或胺得到N-糖基氨基甲酸酯和脲。重排通过 [3,3]-sigmatropic 机制以完全立体选择性发生，根据碳水化合物 C-3 的构型提供 α- 或 β- 连接的胺。
• α-<i>N-</i>Acetylmannosamine (ManNAc) Synthesis via Rhodium(II)-Catalyzed Oxidative Cyclization of Glucal 3-Carbamates
  作者：Rena Bodner、Bridget K. Marcellino、Alexandra Severino、Abigail L. Smenton、Christian M. Rojas

  DOI：10.1021/jo0500129

  日期：2005.5.1

  Glucal 3-carbamates 1 and 7 underwent oxidative cyclization with iodobenzene diacetate or iodosobenzene in the presence of Rh-2(OAc)(4), providing mannosamine 2-N,3-O-oxazolidinones. With iodosobenzene, incorporation of 4-penten-1-ol provided a readily separable anomeric mixture of n-pentenyl glycosides, with the anomers exhibiting pronounced differences in reactivity as glycosyl donors. N-acylation of the sugar oxazolidinones led to a-selective glycosyl donors for the elaboration of various 2-mannosamine frameworks. Alternatively, the anomeric n-pentenyl glycosides of N-Cbz 2-mannosamine oxazolidinones were converted separately to oxazolidinone-opened derivatives 28 alpha and 28 beta. These served as stereoconvergent glycosyl donors, and the a-linked products were readily advanced to a variety of N-acetylmannosamine (ManNAc) frameworks, using an intramolecular O -> N acetyl transfer as the final step.
• Protecting Group and Solvent Control of Stereo- and Chemoselectivity in Glucal 3-Carbamate Amidoglycosylation
  作者：Ritu Gupta、Kimberly M. Sogi、Sarah E. Bernard、John D. Decatur、Christian M. Rojas

  DOI：10.1021/ol900126q

  日期：2009.4.2

  In the Rh-2(OAC)(4)-catalyzed amidoglycosylation of glucal 3-carbamates, anomeric stereoselectivity and the extent of competing C3-H oxidation depend on the 40 and 60 protecting groups. Acyclic protection permits high alpha-anomer selectivity with further improvement in less polar solvents, while electron-withdrawing protecting groups limit C3-oxidized byproducts. Stereocontrol and bifurcation between alkene insertion and C3-H oxidation reflect an interplay of conformational, stereoelectronic, and inductive factors.
• The Disaccharide Moiety of Bleomycin Facilitates Uptake by Cancer Cells
  作者：Benjamin R. Schroeder、M. Imran Ghare、Chandrabali Bhattacharya、Rakesh Paul、Zhiqiang Yu、Paul A. Zaleski、Trevor C. Bozeman、Michael J. Rishel、Sidney M. Hecht

  DOI：10.1021/ja507255g

  日期：2014.10.1

  The disaccharide moiety is responsible for the tumor cell targeting properties of bleomycin (BLM). While the aglycon (deglycobleomycin) mediates DNA cleavage in much the same fashion as bleomycin, it exhibits diminished cytotoxicity in comparison to BLM. These findings suggested that BLM might be modular in nature, composed of tumor-seeking and tumoricidal domains. To explore this possibility, BLM analogues were prepared in which the disaccharide moiety was attached to deglycobleomycin at novel positions, namely, via the threonine moiety or C-terminal substituent. The analogues were compared with BLM and deglycoBLM for DNA cleavage, cancer cell uptake, and cytotoxic activity. BLM is more potent than deglycoBLM in supercoiled plasmid DNA relaxation, while the analogue having the disaccharide on threonine was less active than deglycoBLM and the analogue containing the C-terminal disaccharide was slightly more potent. While having unexceptional DNA cleavage potencies, both glycosylated analogues were more cytotoxic to cultured DU145 prostate cancer cells than deglycoBLM. Dye-labeled conjugates of the cytotoxic BLM aglycons were used in imaging experiments to determine the extent of cell uptake. The rank order of internalization efficiencies was the same as their order of cytotoxicities toward DU145 cells. These findings establish a role for the BLM disaccharide in tumor targeting/uptake and suggest that the disaccharide moiety may be capable of delivering other cytotoxins to cancer cells. While the mechanism responsible for uptake of the BLM disaccharide selectively by tumor cells has not yet been established, data are presented which suggest that the metabolic shift to glycolysis in cancer cells may provide the vehicle for selective internalization.