4-pentenyl 2-amino-(N-3-O-carbonyl)-2-deoxy-4,6-O-(di-tert-butylsilylene)-α-D-mannopyranoside

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 4-pentenyl 2-amino-(N-3-O-carbonyl)-2-deoxy-4,6-O-(di-tert-butylsilylene)-α-D-mannopyranoside
• 英文别名: 4-pentenyl 2-amino-2-N,3-O-carbonyl-2-deoxy-4,6-O-di-tert-butylsilylene-α-D-mannopyranoside；(1S,2R,6S,7S,9R)-12,12-ditert-butyl-7-pent-4-enoxy-3,8,11,13-tetraoxa-5-aza-12-silatricyclo[7.4.0.02,6]tridecan-4-one
• 化学式: C₂₀H₃₅NO₆Si
• 分子量: 413.587
• InChiKey: ZCWWBPVZFHPBBY-JJTUDDRGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.63
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  75.2
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4,6-O-di(tert-butyl)silanediyl-D-glucal 在 dirhodium tetraacetate 亚碘酰苯 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 25.0h， 生成 4-pentenyl 2-amino-(N-3-O-carbonyl)-2-deoxy-4,6-O-(di-tert-butylsilylene)-α-D-mannopyranoside
  参考文献：
  名称：

  α-N-Acetylmannosamine (ManNAc) Synthesis via Rhodium(II)-Catalyzed Oxidative Cyclization of Glucal 3-Carbamates

  摘要：

  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.

  DOI：

  10.1021/jo0500129

文献信息

• 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.
• Dihydropyranone Formation by <i>Ipso</i> C−H Activation in a Glucal 3-Carbamate-Derived Rhodium Acyl Nitrenoid
  作者：Brisa Hurlocker、Nadia C. Abascal、Lindsay M. Repka、Elsy Santizo-Deleon、Abigail L. Smenton、Victoria Baranov、Ritu Gupta、Sarah E. Bernard、Shenjuti Chowdhury、Christian M. Rojas

  DOI：10.1021/jo101599q

  日期：2011.4.1

  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.
• 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.