2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol | 150822-91-6

• 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: 2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol
• 英文别名: [(2R,3S,4S,5S)-3,4,5-triacetyloxy-1,6-dibromohexan-2-yl] acetate
• CAS: 150822-91-6
• 化学式: C₁₄H₂₀Br₂O₈
• 分子量: 476.116
• InChiKey: UKPLTNPGLVFJHC-XJFOESAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  24
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol 在 sodium sulfide 作用下， 以 二甲基亚砜 为溶剂， 反应 0.75h， 以85%的产率得到2,3,4,5-tetra-O-acetyl-1,6-anhydro-1-thio-D-glucitol
  参考文献：
  名称：

  Short and efficient synthesis of polyhydroxylated tetrahydrothiophene, tetrahydrothiopyrane and thiepane from bielectrophilic erythro, threo, xylo, ribo, arabino, manno and gluco α,ω-dibromoalditol derivatives

  摘要：

  Polyhydroxylated tetrahydrothiophene, tetrahydrothiopyrane and thiepane rings have been readily obtained in excellent yields (78-95%) from thioheterocyclisation of the bielectrophilic petacetylated alpha,omega -dibrominated derivatives of tetritols (erythritol (1) and D,L-threitol (4)), pentitols: (xylitol (7), ribitol (10) and D-arabinitol (14)) and hexitols (D-mannitol (17) and D-glucitol (20)), respectively. With 2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol (21) as substrate, the unexpected 2,6-anhydro derivative 25 was obtained. This could be attributed to previous S-= regioselective nucleophilic attack at C-1 position followed by 1,2-transesterification and 2,6-O-heterocyclisation. The preferential attack at C-1 of the D-glucitol derivative 21 subsequently allowed a facile direct synthesis in good yields of 2,3,4,5,6-penta-O-acetyl-1-bromo-1-deoxy-D-glucitol (26), 2,3,4,5-tetra-O-acetyl-6-bromo-6-deoxy-1-thiobutyl-1-deoxy-D-glucitol (28) and 2,3,3,5-tetra-O-acetyl-6-bromo-6-deoxy-1-thiooctyl-1-deoxy-D-glucitol (28). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00442-7
• 作为产物：
  描述：

  乙酸酐 、 1,6-dibromosorbitol 在 吡啶 作用下， 生成 2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol
  参考文献：
  名称：

  Short and efficient synthesis of polyhydroxylated tetrahydrothiophene, tetrahydrothiopyrane and thiepane from bielectrophilic erythro, threo, xylo, ribo, arabino, manno and gluco α,ω-dibromoalditol derivatives

  摘要：

  Polyhydroxylated tetrahydrothiophene, tetrahydrothiopyrane and thiepane rings have been readily obtained in excellent yields (78-95%) from thioheterocyclisation of the bielectrophilic petacetylated alpha,omega -dibrominated derivatives of tetritols (erythritol (1) and D,L-threitol (4)), pentitols: (xylitol (7), ribitol (10) and D-arabinitol (14)) and hexitols (D-mannitol (17) and D-glucitol (20)), respectively. With 2,3,4,5-tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol (21) as substrate, the unexpected 2,6-anhydro derivative 25 was obtained. This could be attributed to previous S-= regioselective nucleophilic attack at C-1 position followed by 1,2-transesterification and 2,6-O-heterocyclisation. The preferential attack at C-1 of the D-glucitol derivative 21 subsequently allowed a facile direct synthesis in good yields of 2,3,4,5,6-penta-O-acetyl-1-bromo-1-deoxy-D-glucitol (26), 2,3,4,5-tetra-O-acetyl-6-bromo-6-deoxy-1-thiobutyl-1-deoxy-D-glucitol (28) and 2,3,3,5-tetra-O-acetyl-6-bromo-6-deoxy-1-thiooctyl-1-deoxy-D-glucitol (28). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00442-7

文献信息

• Peracetylated 1,6-dibromo-d-glucitol as efficient precursor of 1,6-diiodo and some mono-, disubstituted and heterocyclic d-glucitol derivatives
  作者：Sami Halila、Mohammed Benazza、Gilles Demailly

  DOI：10.1016/s0008-6215(02)00421-4

  日期：2003.1

  regioselectivity allowed the synthesis of some mono- and disubstituted derivatives of D-glucitol. Thus, the peracetylated derivatives of D-glucitol, 6-bromo, 6-bromo-1-S-butyl, 6-bromo-1-S-octyl, 6-S-butyl, 6-S-butyl-1-S-octyl, 1-S-butyl, 1,6-di-S-octyl and 6-S-phenyl were synthesised in good to excellent yields. With S= as binucleophilic reagent, 1a gave mainly the thiepane derivative (75%) plus the 1-S-acetyl-2

  由D-葡萄糖醇获得的2,3,4,5-四-O-乙酰基-1,6-二溴-1,6-二脱氧-D-葡萄糖醇（1a）容易转化为1,6-二碘衍生物与过量的碘化钠在丁酮中回流2小时反应，收率（97％）。当反应时间延长至24 h并且粗产物被乙酰化时，分离出1,2,3,4,5-戊五-O-乙酰基-6-脱氧-6-碘-D-葡萄糖醇和D-葡萄糖醇六乙酸酯分别达到50％和26％的产量。然后在C-1区域选择性地进行单脱卤。这种区域选择性允许合成D-葡萄糖醇的一些单取代和二取代的衍生物。因此，D-葡萄糖醇，6-溴，6-溴-1-S-丁基，6-溴-1-S-辛基，6-S-丁基，6-S-丁基-1-S-的全乙酰化衍生物。合成了辛基，1-S-丁基，1,6-二-S-辛基和6-S-苯基，收率良好。
• Synthesis of α,ω‐Diazidoalditol Derivatives via Both <i>bis</i>‐ or <i>tris</i>‐Cyclic Sulfites and Peracetylated α,ω‐Dibromoalditols as Bielectrophilic Intermediates
  作者：Virginie Glaçon、Mohammed Benazza、Aniss El Anzi、Daniel Beaupère、Gilles Demailly

  DOI：10.1081/car-120030470

  日期：2004.12.26

  The alpha,omega-diazidoalditol derivatives with erythro, threo, xylo, ribo, D-arabino, D-manno, and D-gluco configuration were efficiently synthesized, respectively, from bis- or tris-cyclic sulfite or peracetylated alpha,omega-dibromoalditol intermediates. The cyclic sulfite intermediates has the advantage to lead directly to the free alpha,omega-diazido-alpha,omega-dideoxyalditols.
• Efficient synthesis of α,ω-dibromodideoxyalditols as precursors for α,ω-dithioalkylalditols
  作者：Caroline Crombez-Robert、Mohammed Benazza、Catherine Fréchou、Gilles Demailly

  DOI：10.1016/s0008-6215(97)00151-1

  日期：1997.9

  The regioselective bromination of unprotected alditols (D-arabinitol, xylitol, ribitol, D-glucitol, and D-mannitol) was achieved with acetyl bromide as the brominating reagent. The alpha,omega-dibromodideoxyalditols were isolated after acetylation in good overall yields (51-80%). 1,5-Dithioalkylpentitols, 1,6-dithioalkyl-D-mannitol, and D-glucitol were obtained from the dibromo derivatives and sodium alkanethiolates (with R = n-butyl, n-octyl, n-dodecyl, and n-hexadecyl). (C) 1997 Published by Elsevier Science Ltd.
• Alditol thiacrowns via a ring-closing metathesis of carbohydrate-derived α,ω-dithioallylethers
  作者：Mohammed Benazza、Alain Danquigny、Guy Novogrocki、Luca Valgimigli、Riccardo Amorati、Fiammetta Ferroni、Catherine Demailly-Mullie、Aloysius Siriwardena、David Lesur、Frédérick Aubry、Gilles Demailly

  DOI：10.1016/j.tet.2015.06.049

  日期：2015.8

  We report a newly developed synthesis of a number of alditol thiacrowns using an eco-friendly and versatile two-step strategy: the regioselective thioallyletherification of a polyhydroxylated alditol followed by a ring closing metathesis using the Grubbs second generation catalyst. This approach allows a series of target thiacrown products to be obtained in acceptable to good yields, from the corresponding alpha-omega-dithioallylether alditol starting materials featuring either the xylo, ribo, threo, erythro, D-manno or D-gluco configurations. The per-O-acetylated D-mannitol dithioallyether 10, easily obtained on a large scale using this approach, was selected for evaluation as both an antibacterial and an antioxidant Although no antibacterial activity was observed for the bacterial strains investigated, compound 10 is shown to be an antioxidant, and able to quench hydrogen peroxide in a stoichiometric fashion. (C) 2015 Elsevier Ltd. All rights reserved.
• Bromation régiosélective d'itols non protégés
  作者：Aniss El Anzi、Mohammed Benazza、Catherine Fréchou、Gilles Demailly

  DOI：10.1016/s0040-4039(00)79215-x

  日期：1993.6

  Hydrobromide acid in acetic acid or 1-bromocarbonyl-1-methyl-ethylacetate allows the transformation of unprotected pentitols and hexitols into linear 1,5 and 1,6-dibromo derivatives in high yields.