tert-butyldimethylsilyl 6-O-acetyl-5-deoxy-5-C-methylidene-2,3:7,8-di-O-isopropylidene-D-glycero-L-talo-α-octofuranoside | 129893-44-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyldimethylsilyl 6-O-acetyl-5-deoxy-5-C-methylidene-2,3:7,8-di-O-isopropylidene-D-glycero-L-talo-α-octofuranoside
• 英文别名: [(1R)-2-[(3aR,4S,6R,6aR)-4-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-6-yl]-1-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enyl] acetate
• CAS: 129893-44-3
• 化学式: C₂₃H₄₀O₈Si
• 分子量: 472.651
• InChiKey: JZLLOKRWEISRTO-PJBUMPDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  32.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  81.68
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  tert-butyldimethylsilyl 6-O-acetyl-5-deoxy-5-C-methylidene-2,3:7,8-di-O-isopropylidene-D-glycero-L-talo-α-octofuranoside 在 lithium aluminium tetrahydride 、 二甲基硫 、 臭氧 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 1.33h， 生成 D-threo-D-allo-octose
  参考文献：
  名称：

  Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. XII. Highly stereoselective total syntheses of octoses and derivatives

  摘要：

  Mukaiyama cross aldolizations of (R)-2,3-O-isopropylideneglyceraldehyde (10) with (1R,4S,5R,6R)-5-exo, 6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-8) were highly diastereoselective and led to the corresponding u,u,l or SYNCAT ((+)-11) and u,u,u or ANCAT ((-)-21) aldols, respectively. The results were interpreted in terms of extended open transition state models with (ul,lk) and (ul,ul) topicities, respectively, which minimize steric repulsions. Aldols (+)-11 and (-)-21 were converted into (tert-butyl)dimethylsilyl 6-O-acetyl-2,3:7, 8-di-O-isopropylidene-D-glycero-L-talo-alpha-octofuranosid-5-ulose ((-)-18) and its D-talo diastereomer ((+)-28), respectively. Reduction of (-)-18 with LiEt3BH in THF gave, after deprotection, the known D-threo-L-talo-octose ((-)-4). Reduction of (-)-18 with (i-Bu)2AlH/THF gave, after deprotection, the unknown D-threo-D-allo-octose ((+)-5) with high stereoselectivity. Similarly, the unknown D-erythro-D-talo-octose ((+)-6) and D-erythro-L-allo-octose ((-)-7) were derived from (+)-28 through reduction with LiB(s-Bu)3H and (i-Bu)2AlH, respectively.

  DOI：

  10.1021/jo00003a041
• 作为产物：
  描述：

  tert-butyldimethylsilyl 6-O-acetyl-5-deoxy-5-C-(((2-nitrophenyl)selenyl)methyl)-2,3:7,8-di-O-isopropylidene-D-threo-L-talo-α-octofuranoside 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以87%的产率得到tert-butyldimethylsilyl 6-O-acetyl-5-deoxy-5-C-methylidene-2,3:7,8-di-O-isopropylidene-D-glycero-L-talo-α-octofuranoside
  参考文献：
  名称：

  Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. XII. Highly stereoselective total syntheses of octoses and derivatives

  摘要：

  Mukaiyama cross aldolizations of (R)-2,3-O-isopropylideneglyceraldehyde (10) with (1R,4S,5R,6R)-5-exo, 6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-8) were highly diastereoselective and led to the corresponding u,u,l or SYNCAT ((+)-11) and u,u,u or ANCAT ((-)-21) aldols, respectively. The results were interpreted in terms of extended open transition state models with (ul,lk) and (ul,ul) topicities, respectively, which minimize steric repulsions. Aldols (+)-11 and (-)-21 were converted into (tert-butyl)dimethylsilyl 6-O-acetyl-2,3:7, 8-di-O-isopropylidene-D-glycero-L-talo-alpha-octofuranosid-5-ulose ((-)-18) and its D-talo diastereomer ((+)-28), respectively. Reduction of (-)-18 with LiEt3BH in THF gave, after deprotection, the known D-threo-L-talo-octose ((-)-4). Reduction of (-)-18 with (i-Bu)2AlH/THF gave, after deprotection, the unknown D-threo-D-allo-octose ((+)-5) with high stereoselectivity. Similarly, the unknown D-erythro-D-talo-octose ((+)-6) and D-erythro-L-allo-octose ((-)-7) were derived from (+)-28 through reduction with LiB(s-Bu)3H and (i-Bu)2AlH, respectively.

  DOI：

  10.1021/jo00003a041

文献信息

• Synthesis of higher-carbon sugars via cross-aldolization of 7-oxanorbornan-2-one and carbohydrate aldehyde derivatives
  作者：Suruliappa Jeganathan、Pierre Vogel

  DOI：10.1039/c39890000993

  日期：——

  The TiCl4-induced condensation of (+)-(1S,4S,5S,6S)-5,6-isopropylidenedioxy-2-t-butyldimethylsilyloxy-7-oxabicyclo[2.2.1]hept-2-ene with 2,3-O-isopropylidene-D-glyceraldehyde was highly stereoselective, giving a product that was converted with high stereoselectivity into protected D-erythro-D-talo-octose and D-erthro-L-allo-octose.

  TiCl 4诱导的（+）-（1 S，4 S，5 S，6 S）-5,6-异丙基二烯二氧基-2-叔丁基二甲基甲硅烷氧基-7-氧杂双环[2.2.1]庚-2-烯的缩合与2,3- ö异亚丙基d甘油醛是高度立体选择性，从而，将其转变高立体选择性成保护的产品d -赤- d -距骨-octose和d - erthro -大号-异体-octose。
• Total synthesis of branched-chain higher-carbon sugars. First synthesis of caldose, calditol and 4-deoxycalditol stereoisomers.
  作者：Suruliappa Jeganathan、Pierre Vogel

  DOI：10.1016/s0040-4039(00)88862-0

  日期：1990.1

  4-C-hydroxymethyl-L-erythro-L-galacto-octitol and 4-deoxy-4-C-hydroxymethylL-erythro-L-gluco-octitol have been derived from D-glyceraldehyde and (+)-(1R,4R)-7-oxabicyclo[2.2.1] hept-5-en-2-one (“naked sugar”).

  5-C-羟甲基-D-苏-D-卤代八糖，5-C-羟甲基-D-苏-L-talo-八糖，4-C-羟甲基-L-赤型-L-葡萄糖-辛醇，4- C-羟甲基-L-赤型-L-半乳糖辛醇和4-脱氧-4-C-羟甲基L-赤型-L-葡萄糖辛醇已衍生自D-甘油醛和（+）-（1R，4R）-7 -oxabicyclo [2.2.1] hept-5-en-2-one（“裸糖”）。
• JEGANATHAN, SURULIAPPA;VOGEL, PIERRE, TETRAHEDRON LETT., 31,(1990) N2, C. 1717-1720
  作者：JEGANATHAN, SURULIAPPA、VOGEL, PIERRE

  DOI：——

  日期：——
• JEGANATHAN, SURULIAPPA;VOGEL, PIERRE, J. ORG. CHEM., 56,(1991) N, C. 1139-1142
  作者：JEGANATHAN, SURULIAPPA、VOGEL, PIERRE

  DOI：——

  日期：——