(S)-(tert-Butyl-diphenyl-silanyloxy)-((4R,5S,4'S)-2,2,2',2'-tetramethyl-[4,4']bi[[1,3]dioxolanyl]-5-yl)-acetaldehyde | 192753-75-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-(tert-Butyl-diphenyl-silanyloxy)-((4R,5S,4'S)-2,2,2',2'-tetramethyl-[4,4']bi[[1,3]dioxolanyl]-5-yl)-acetaldehyde
• 英文别名: (2S)-2-[tert-butyl(diphenyl)silyl]oxy-2-[(4S,5R)-5-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]acetaldehyde
• CAS: 192753-75-6
• 化学式: C₂₈H₃₈O₆Si
• 分子量: 498.692
• InChiKey: UGTRPMKJRLWRNI-ZFFYZDHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  35
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  溴甲苯 、 (S)-(tert-Butyl-diphenyl-silanyloxy)-((4R,5S,4'S)-2,2,2',2'-tetramethyl-[4,4']bi[[1,3]dioxolanyl]-5-yl)-acetaldehyde 在 四丁基氟化铵 、 sodium hydride 、 溶剂黄146 作用下， 生成 benzyl 2,3,5-tri-O-benzyl-α-L-gulofuranoside
  参考文献：
  名称：

  Carbohydrate Homologation by the Use of 2-(Trimethylsilyl)thiazole. Preparative Scale Synthesis of Rare Sugars:  l-Gulose, l-Idose, and the Disaccharide Subunit of Bleomycin A₂

  摘要：

  The well established one-carbon homologation method of protected monosaccharides employing 2-(trimethylsilyl)thiazole (2-TST) as a formyl anion equivalent has been used for high yield and multigram scale synthesis of the title rare hexoses from L-xylose. Thus, L-gulose has been obtained by stereoselective anti-addition of 2-TST to aldehydo-L-xylose diacetonide followed by thiazole to formyl conversion of the resulting alcohol. The inversion of configuration at C-1 of this alcohol by an oxidation-reduction sequence prior to the aldehyde releasing from thiazole led to L-idose. The same alcohol was readily elaborated into 1,3,4,6-tetra-O-acetyl-L-gulopyranose whose highly stereoselective glycosidation coupling with 3-O-carbamoyl-2,4,6-tri-O-acetyl-alpha-D-mannosyl diethyl phosphate afforded the same peracetylated disaccharide subunit employed by Boger and Honda in the total synthesis of the antibiotic bleomycin A(2).

  DOI：

  10.1021/jo970601h
• 作为产物：
  描述：

  L-木糖 在 咪唑 、 盐酸 、 sodium tetrahydroborate 、 4 A molecular sieve 、 四丁基氟化铵 、 mercury dichloride 、 copper(II) oxide 、 mercury(II) oxide 作用下， 以 水 、 N,N-二甲基甲酰胺 、 丙酮 、 乙腈 为溶剂， 反应 32.33h， 生成 (S)-(tert-Butyl-diphenyl-silanyloxy)-((4R,5S,4'S)-2,2,2',2'-tetramethyl-[4,4']bi[[1,3]dioxolanyl]-5-yl)-acetaldehyde
  参考文献：
  名称：

  Carbohydrate Homologation by the Use of 2-(Trimethylsilyl)thiazole. Preparative Scale Synthesis of Rare Sugars:  l-Gulose, l-Idose, and the Disaccharide Subunit of Bleomycin A₂

  摘要：

  The well established one-carbon homologation method of protected monosaccharides employing 2-(trimethylsilyl)thiazole (2-TST) as a formyl anion equivalent has been used for high yield and multigram scale synthesis of the title rare hexoses from L-xylose. Thus, L-gulose has been obtained by stereoselective anti-addition of 2-TST to aldehydo-L-xylose diacetonide followed by thiazole to formyl conversion of the resulting alcohol. The inversion of configuration at C-1 of this alcohol by an oxidation-reduction sequence prior to the aldehyde releasing from thiazole led to L-idose. The same alcohol was readily elaborated into 1,3,4,6-tetra-O-acetyl-L-gulopyranose whose highly stereoselective glycosidation coupling with 3-O-carbamoyl-2,4,6-tri-O-acetyl-alpha-D-mannosyl diethyl phosphate afforded the same peracetylated disaccharide subunit employed by Boger and Honda in the total synthesis of the antibiotic bleomycin A(2).

  DOI：

  10.1021/jo970601h

文献信息

• Carbohydrate Homologation by the Use of 2-(Trimethylsilyl)thiazole. Preparative Scale Synthesis of Rare Sugars:  <scp>l</scp>-Gulose, <scp>l</scp>-Idose, and the Disaccharide Subunit of Bleomycin A₂
  作者：Alessandro Dondoni、Alberto Marra、Alessandro Massi

  DOI：10.1021/jo970601h

  日期：1997.9.1

  The well established one-carbon homologation method of protected monosaccharides employing 2-(trimethylsilyl)thiazole (2-TST) as a formyl anion equivalent has been used for high yield and multigram scale synthesis of the title rare hexoses from L-xylose. Thus, L-gulose has been obtained by stereoselective anti-addition of 2-TST to aldehydo-L-xylose diacetonide followed by thiazole to formyl conversion of the resulting alcohol. The inversion of configuration at C-1 of this alcohol by an oxidation-reduction sequence prior to the aldehyde releasing from thiazole led to L-idose. The same alcohol was readily elaborated into 1,3,4,6-tetra-O-acetyl-L-gulopyranose whose highly stereoselective glycosidation coupling with 3-O-carbamoyl-2,4,6-tri-O-acetyl-alpha-D-mannosyl diethyl phosphate afforded the same peracetylated disaccharide subunit employed by Boger and Honda in the total synthesis of the antibiotic bleomycin A(2).