phenyl 2,3,4-tri-O-benzoyl-6-O-tert-butyldimethytylsilyl-1-thio-β-D-galactopyranoside | 212128-07-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3,4-tri-O-benzoyl-6-O-tert-butyldimethytylsilyl-1-thio-β-D-galactopyranoside
• 英文别名: Bz(-2)[Bz(-3)][Bz(-4)][TBDMS(-6)]Gal(b)-SPh；[(2R,3S,4S,5R,6S)-4,5-dibenzoyloxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-phenylsulfanyloxan-3-yl] benzoate
• CAS: 212128-07-9
• 化学式: C₃₉H₄₂O₈SSi
• 分子量: 698.909
• InChiKey: RMSVJFLLATWZEE-NNQVOBLHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  49
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  123
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4-tri-O-benzoyl-6-O-tert-butyldimethytylsilyl-1-thio-β-D-galactopyranoside 在 盐酸 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 0.5h， 以97%的产率得到phenyl 2,3,4-tri-O-benzoyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Scope and Applications of "Active and Latent" Thioglycosyl Donors. Part 4

  摘要：

  The relative reactivity of various thioglycosyl donors having ethyl, phenyl, or parasubstituted phenyl groups with electron donating (N-Ac) or electron withdrawing (NO2) substituents were compared using 1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (3) as standard glycosyl acceptor. The reactivity order was found to decrease from ethyl > phenyl > p-acetamidophenyl > p-nitrophenyl. In the latter situation, when the thioglycosyl donor was also equipped with "disarming" ester protecting groups, they were found to be inert or inactive toward common thiophilic promoters. Alternatively, it was possible to selectively activate the "armed" perbenzylated p-nitrophenyl 1-thio-beta-D-galactopyranoside (21) in the presence of the corresponding "disarmed" perbenzoylated p-nitrophenyl 2,3,4-tri-O-benzoyl-1-thio-beta-D-galactopyranoside (15) which served as the glycosyl acceptor. When both "armed" perbenzylated thioglycosides 7 and 25 were used as thioglycosyl donor and thioglycosyl acceptor, respectively, the milder thiophilic promotor methyl triflate was required for chemoselective activation. These results further demonstrate the potential of "armed and disarmed" "active and latent" thioglycosides in blockwise oligosaccharide syntheses.

  DOI：

  10.1080/07328309808002341
• 作为产物：
  描述：

  苯基-1-硫醇-beta-D-半乳糖苷 以 吡啶 为溶剂， 反应 6.5h， 生成 phenyl 2,3,4-tri-O-benzoyl-6-O-tert-butyldimethytylsilyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Scope and Applications of "Active and Latent" Thioglycosyl Donors. Part 4

  摘要：

  The relative reactivity of various thioglycosyl donors having ethyl, phenyl, or parasubstituted phenyl groups with electron donating (N-Ac) or electron withdrawing (NO2) substituents were compared using 1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (3) as standard glycosyl acceptor. The reactivity order was found to decrease from ethyl > phenyl > p-acetamidophenyl > p-nitrophenyl. In the latter situation, when the thioglycosyl donor was also equipped with "disarming" ester protecting groups, they were found to be inert or inactive toward common thiophilic promoters. Alternatively, it was possible to selectively activate the "armed" perbenzylated p-nitrophenyl 1-thio-beta-D-galactopyranoside (21) in the presence of the corresponding "disarmed" perbenzoylated p-nitrophenyl 2,3,4-tri-O-benzoyl-1-thio-beta-D-galactopyranoside (15) which served as the glycosyl acceptor. When both "armed" perbenzylated thioglycosides 7 and 25 were used as thioglycosyl donor and thioglycosyl acceptor, respectively, the milder thiophilic promotor methyl triflate was required for chemoselective activation. These results further demonstrate the potential of "armed and disarmed" "active and latent" thioglycosides in blockwise oligosaccharide syntheses.

  DOI：

  10.1080/07328309808002341

文献信息

• Synthesis of a new glycosphingolipid, neurosporaside, from Neurospora crassa
  作者：Isao Ohtsuka、Noriyasu Hada、Misaki Kanemaru、Takanari Fujii、Toshiyuki Atsumi、Nobuko Kakiuchi

  DOI：10.1016/j.carres.2014.11.018

  日期：2015.3

  The glycosphingolipid neurosporaside (alpha-D-Glcp-(1 -> 2)-beta-D-Galp-(1 -> 6)-beta-D-Galp-(1 -> 6)-beta-D-Galp-(1 ->)-Cer) occurs in Neurospora crassa. We attempted to synthesize neurosporaside by block synthesis (route A) and linear synthesis (route B). Oligosaccharide derivatives were synthesized using trimethylsilyltrifluoromethanesulfonate and N-iodosuccinimide/trifluoromethane sulfonic acid as promoters. The target tetrasaccharide could not be attained via route A, but route B showed potential: glycosidic bonds (beta-D-Galp-(1 -> 6)-beta-D-Galp-(1 -> 6)-beta-D-Galp) were formed stereoselectively, leading to the synthesis of glycosphingolipid 2. (C) 2014 Elsevier Ltd. All rights reserved.
• Scope and Applications of "Active and Latent" Thioglycosyl Donors. Part 4
  作者：Suoding Cao、Fernando Hernández-Matéo、René Roy

  DOI：10.1080/07328309808002341

  日期：1998.5.1

  The relative reactivity of various thioglycosyl donors having ethyl, phenyl, or parasubstituted phenyl groups with electron donating (N-Ac) or electron withdrawing (NO2) substituents were compared using 1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose (3) as standard glycosyl acceptor. The reactivity order was found to decrease from ethyl > phenyl > p-acetamidophenyl > p-nitrophenyl. In the latter situation, when the thioglycosyl donor was also equipped with "disarming" ester protecting groups, they were found to be inert or inactive toward common thiophilic promoters. Alternatively, it was possible to selectively activate the "armed" perbenzylated p-nitrophenyl 1-thio-beta-D-galactopyranoside (21) in the presence of the corresponding "disarmed" perbenzoylated p-nitrophenyl 2,3,4-tri-O-benzoyl-1-thio-beta-D-galactopyranoside (15) which served as the glycosyl acceptor. When both "armed" perbenzylated thioglycosides 7 and 25 were used as thioglycosyl donor and thioglycosyl acceptor, respectively, the milder thiophilic promotor methyl triflate was required for chemoselective activation. These results further demonstrate the potential of "armed and disarmed" "active and latent" thioglycosides in blockwise oligosaccharide syntheses.