3,7-anhydro-1-C-bromo-1,2,6-trideoxy-6-C-<propyl>silyl>ethynyl>-4-O-(triisopropylsilyl)-D-glycero-D-gulo-oct-1-ynitol | 221189-33-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,7-anhydro-1-C-bromo-1,2,6-trideoxy-6-C-<propyl>silyl>ethynyl>-4-O-(triisopropylsilyl)-D-glycero-D-gulo-oct-1-ynitol
• 英文别名: (2S,3R,4S,5S,6S)-2-(2-bromoethynyl)-5-[2-[dimethyl-[2-methyl-4-tri(propan-2-yl)silyloxybutan-2-yl]silyl]ethynyl]-6-(hydroxymethyl)-3-tri(propan-2-yl)silyloxyoxan-4-ol
• CAS: 221189-33-9
• 化学式: C₃₅H₆₇BrO₅Si₃
• 分子量: 732.074
• InChiKey: UYQFDINETWLNOZ-BBZHULIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.25
• 重原子数：
  44
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,7-anhydro-1-C-bromo-1,2,6-trideoxy-6-C-<propyl>silyl>ethynyl>-4-O-(triisopropylsilyl)-D-glycero-D-gulo-oct-1-ynitol 在 tris-(dibenzylideneacetone)dipalladium(0) 、 copper(l) iodide 、 P(fur)3 、 三乙胺 作用下， 以 二甲基亚砜 、 1,2-二氯乙烷 为溶剂， 反应 37.0h， 生成 5,9-anhydro-1,2,3,4,8-pentadeoxy-8-C-<<<1,1-dimethyl-3-<(triisopropylsilyl)oxy>propyl>dimethylsilyl>ethynyl>-7,10-bis-O-(methoxymethyl)-6-O-(triisopropylsilyl)-D-glycero-D-gulo-deca-1,3-diynitol-1-yl-(1->6-C)-3,7-anhdyro-1,2,6-trideoxy-4-O-(triisopro...
  参考文献：
  名称：

  Oligosaccharide Analogues of Polysaccharides, Part 17, Synthesis and Characterization of a Hexadecamer: Evidence for the Essential Structural Role of the Intramolecular, Interresidue C(3)−OH⋅⋅⋅O−C(5) Hydrogen Bond in Celluloses

  摘要：

  The hexadecamer 63 dissolves readily in DMSO and shows no sign of association, in agreement with the essential structural role of the intramolecular, interresidue C(3)-OH ... O-C(5) H-bond of celluloses, MM3 Calculations predict a rod-like shape for the cello-oligosaccharides In agreement with this, nanocrystalline domains of parallel chains are observed by high-resolution electron microscopy (HREM) for 54 and 63 on carbon-coated copper grids. For the synthesis of the hexadecamer 54, we studied the influence of protecting groups on the cross-coupling of acetyleno-oligosaccharides and on their solubility (Scheme 2). The octamer 12 derived from the minimally O-protected monomer 2 is insoluble, while the methoxymethyl- and triisopropysilyl-protected hexadecamer 54 prepared in twelve steps from the dimer 41 (Scheme 4), is readily soluble in a variety of solvents. O- and C-deprotection of 54 led in four steps and in 76% yield to the hexadecamer 63 (Schemes 5 and 6). There is only a small difference of spectroscopic properties between the protected octamer 50 and hexadecamer 54, and, similarly, between the unprotected octamer 64 and hexadecamer 63 (Fig. 3).

  DOI：

  10.1002/(sici)1522-2675(19990210)82:2<198::aid-hlca198>3.0.co;2-y
• 作为产物：
  描述：

  1,6-anhydro-4-deoxy-4-C-propyl>silyl>ethynyl>-2-O-(triisopropylsilyl)-β-D-glucopyranose 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 三氯化铝 、 sodium methylate 、 silver trifluoroacetate 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 22.5h， 生成 3,7-anhydro-1-C-bromo-1,2,6-trideoxy-6-C-<propyl>silyl>ethynyl>-4-O-(triisopropylsilyl)-D-glycero-D-gulo-oct-1-ynitol
  参考文献：
  名称：

  Oligosaccharide Analogues of Polysaccharides, Part 16, Cross-Coupling of Partially Protected Dialkynyl Monosaccharides

  摘要：

  The dependency of the cross-coupling of orthogonally C-protected dialkynyl monosaccharides on the nature of the coupling partners has been studied, The required dialkyne 5 was synthesized from levoglucosan in six steps and 39% overall yield and transformed into 7 10, 12, 13, and 14 by orthogonal C-deprotection and bromination (Scheme 1). Optimization of the conditions of their cross-coupling to 16 showed that yields were higher for the coupling of the propargylic bromoalkyne 10 than for the homopropargylic bromoalkyne 14 (Scheme 2). Deprotection of 16 gave the nano-crystalline dimer 20. To obtain more highly crystalline products, the monomers 7 and 13 were coupled with 1-iodo-4-nitrobenzene to the arylated monomers 21 and 24 (Scheme 3). The 4-NO2C6H4, substituent lowered the yield of the dimerizations to the mono- and diarylated dimers 26-28 (Scheme 4) but had no effect on crystallinity.

  DOI：

  10.1002/(sici)1522-2675(19990210)82:2<143::aid-hlca143>3.0.co;2-0