1,2-dideoxy-4,6-di-tert-butylsilylene-D-erythro-hex-1-enopyran-3-ulose

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 1,2-dideoxy-4,6-di-tert-butylsilylene-D-erythro-hex-1-enopyran-3-ulose
• 英文别名: (4aR,8aR)-2,2-di-tert-butyl-4,4a-dihydropyrano[3,2-d][1,3,2]dioxasilin-8(8aH)-one；1,2-dideoxy-4,6-O-(di-tert-butylsilylene)-D-erythro-hex-1-enopyran-3-ulose；(4aR,8aR)-2,2-ditert-butyl-4a,8a-dihydro-4H-pyrano[3,2-d][1,3,2]dioxasilin-8-one
• 化学式: C₁₄H₂₄O₄Si
• 分子量: 284.428
• InChiKey: VGVULAFSSQQVRQ-NEPJUHHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.93
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-dideoxy-4,6-di-tert-butylsilylene-D-erythro-hex-1-enopyran-3-ulose 在 咪唑 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 四丙基高钌酸铵 、 四丁基氟化铵 、 copper(l) cyanide 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 、 三乙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.67h， 生成
  参考文献：
  名称：

  第一次全合成6-表-表叶薄荷醇

  摘要：

  我们描述6-一种新型高效全合成外延自市售三-phomonol Ø乙酰基d -glucal。合成的关键特征包括使用氰基高锰酸镁的立体选择性迈克尔加成。

  DOI：

  10.1016/j.tetlet.2016.05.006
• 作为产物：
  描述：

  4,6-O-di(tert-butyl)silanediyl-D-glucal 在 重铬酸吡啶 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以97%的产率得到1,2-dideoxy-4,6-di-tert-butylsilylene-D-erythro-hex-1-enopyran-3-ulose
  参考文献：
  名称：

  A Concise, Enantioselective Synthesis of (+)-Decarestrictine L from Tri-O-acetyl-d-glucal

  摘要：

  我们介绍了一种基于立体选择性迈克尔加成法从市售的三-O-乙酰基-d-葡萄糖醛中对映体选择性合成 (+)-(2R,3S,6R)-decarestrictine L 的高效新方法。

  DOI：

  10.1055/s-0029-1218774

文献信息

• 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.
• 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.