(1R,4R,5S,6S,7S)-4-exo-<(1'S,2'R)-1'-Hydroxy-2',3'-(isopropylidenedioxy)propyl>-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo<3.2.1>octan-3-one | 125284-31-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4R,5S,6S,7S)-4-exo-<(1'S,2'R)-1'-Hydroxy-2',3'-(isopropylidenedioxy)propyl>-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo<3.2.1>octan-3-one
• 英文别名: (1R,4R,5S,6S,7S)-4-exo-((1'S,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo<3.2.1>octan-2-one；(1S,2S,6S,7R,10R)-10-[(S)-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]-4,4-dimethyl-3,5,8,11-tetraoxatricyclo[5.3.1.02,6]undecan-9-one
• CAS: 125284-31-3；129830-02-0
• 化学式: C₁₅H₂₂O₈
• 分子量: 330.335
• InChiKey: YZFCSGRQWPFYAV-SQYOGTBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1R,4R,5S,6S,7S)-4-exo-<(1'S,2'R)-1'-Hydroxy-2',3'-(isopropylidenedioxy)propyl>-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo<3.2.1>octan-3-one 在 palladium on activated charcoal 2,6-二甲基吡啶 、 氢气 、 cesium fluoride 作用下， 以 二氯甲烷 、 二甲基亚砜 、 乙酸乙酯 为溶剂， 生成
  参考文献：
  名称：

  Total syntheses of 1,5-dideoxy-1,5-imino-D-erythro-L-allo-octitol and (1S,2R,6R,7R,8S,8aS)-pentahydroxyindolizidine

  摘要：

  DOI：

  10.1016/s0040-4039(00)61233-9
• 作为产物：
  描述：

  (1R,3S,4R,5R,6R)-3-exo-((1'R,2'R)-1'-hydroxy-2',3'-(isopropylidenedioxy)propyl)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>heptan-2-one 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到(1R,4R,5S,6S,7S)-4-exo-<(1'S,2'R)-1'-Hydroxy-2',3'-(isopropylidenedioxy)propyl>-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo<3.2.1>octan-3-one
  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 Asymmetric Syntheses of 1,5-Dideoxy-1,5-iminooctitols and 1,2,6,7,8-Pentahydroxyindolizidines
  作者：Yuanwei Chen、Pierre Vogel

  DOI：10.1021/jo00088a033

  日期：1994.5

  (1R,4R,5S,6S,7S)-4-exo-[(1'S,2'R)-1'-Hydroxy-2',3'-(isopropylidenedioxy)propyl]-6-exo,7-exo-(isopropylidenedioxy)-2,8-dioxabicyclo[3.2.1]octan-3-one ((+)-5) and its diastereomer (1S,4S,5R,6R,7R)-(1'R,2'R)-(-)-30 derived from (R)-2,3-O-isopropylideneglyceraldehyde and (+/-)-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]hept-2-one were alcoholyzed with benzyl alcohol in CCl4 (CsF as base) into the corresponding 5-C-(benzyloxycarbonly)-5-deoxyoctofuranoses (+)-9 and (-)-31 which were converted via Curtius rearrangements into (-)-1,5-dideoxy-1,5-imino-D-erythro-D-talo-octitol ((-)-20) and its D-threo-L-talo isomer (+)-36, respectively, Alcoholyses of (+)-5 and (-)-30 with benzyl alcohol in DMSO in the presence of CsF or K2CO3 led to the epimerized benzyl esters (-)-10 and (-)-38, respectively, which were converted into (-)-1,5-didoexy-1,5-imino-D-erythro-6-allo-octitol ((-)-27) and its D-threo-D-allo isomer (+)-42. The 1,5-dideoxy-1,5-iminooctitols were converted into the corresponding 1,2,6,7,8-pentahydroxyindolizidines in a single step.

  (1R,4R,5S,6S,7S)-4-exo-[(1'S,2'R)-1'-羟基-2',3'-(异丙叉二氧基)丙基]-6-exo,7-exo-(异丙叉二氧基)-2,8-二氧杂双环[3.2.1]辛烷-3-酮 ((+)-5) 及其对映体 (1S,4S,5R,6R,7R)-(1'R,2'R)-(-)-30，源自 (R)-2,3-O-异丙叉甘油醛和 (+/-)-5-exo,6-exo-(异丙叉二氧基)-7-氧杂双环[2.2.1]庚-2-酮，经在四氯化碳（铯氟化物作为碱）中与苯甲醇进行醇解，生成相应的 5-C-(苯甲氧基羰基)-5-去氧代八糖呋喃糖苷 (+)-9 和 (-)-31。后者经卡特里乌斯重排转化为 (-)-1,5-二去氧-1,5-亚胺-D-赤-L-塔罗八糖醇 ((-)-20) 和其 D-赤-L-塔罗异构体 (+)-36。此外，(+)-5 和 (-)-30 在二甲基亚砜中、在铯氟化物或碳酸钾存在下与苯甲醇醇解，生成构型互变的苯甲酸酯 (-)-10 和 (-)-38，进而转化为 (-)-1,5-二去氧-1,5-亚胺-D-赤-6-阿洛八糖醇 ((-)-27) 和其 D-赤-D-阿洛异构体 (+)-42。1,5-二去氧-1,5-亚胺八糖醇随后单步转化为相应的 1,2,6,7,8-五羟基吲哚嗪。
• JEGANATHAN, SURULIAPPA;VOGEL, PIERRE, J. CHEM. SOC. CHEM. COMMUN.,(1989) N5, C. 993-995
  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：——