(-)-2-<<(tert-butyl)dimethylsilyl>oxy>-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-ene | 123155-44-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-2-<<(tert-butyl)dimethylsilyl>oxy>-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-ene
• 英文别名: (-)-2-{[(tert-butyl)dimethylsilyl]oxy}-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo[2.2.1]hept-2-ene；tert-butyl-[[(1R,2R,6R,7R)-4,4-dimethyl-3,5,10-trioxatricyclo[5.2.1.02,6]dec-8-en-8-yl]oxy]-dimethylsilane
• CAS: 123155-44-2；123238-11-9；123238-12-0
• 化学式: C₁₅H₂₆O₄Si
• 分子量: 298.455
• InChiKey: VPMFVKKXUXNMAK-MGAJPHDKSA-N

物化性质

• 沸点：
  319.1±42.0 °C(predicted)
• 密度：
  1.07±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (-)-2-<<(tert-butyl)dimethylsilyl>oxy>-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-ene 以 二氯甲烷 、 乙腈 为溶剂， 反应 37.5h， 生成 (+/-)-2-endo/exo-<<(tert-butyl)dimethylsilyl>oxy>-3-exo-amino>-5-exo,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-exo/endo-yl acetate
  参考文献：
  名称：

  完全不对称合成脱氧多毒素C

  摘要：

  从呋喃的Diels-Alder加合物16到1-氰基乙烯基（1S'）-樟脑酸酯脱氧多恶菌素C（4）的起始步骤已分11步获得，总产率为4.8％，并回收了手性助剂（（1S）-樟脑酸）在合成的早期阶段。该方法意味着将（-）-2-（叔丁基）二甲基甲硅烷基]氧基-5-exo6-exo-（异丙基二烯二氧基）-7-氧杂双环[2.2.1]庚-2-烯（-）- 12溴化并其高度立体选择性转化为（-）-苄基（123-O-三乙酰基-5-叠氮基5-脱氧-ga-和β-D-呋喃呋喃糖苷）-尿酸酯（9）。还介绍了用含氮部分对S-exo6-exo-（异丙基二烯二氧基）-7-氧杂双环[2.2.1]庚-2--2-（（+-）- 11）中的C（3）进行立体选择性取代的程序。

  DOI：

  10.1016/s0040-4020(01)87887-x
• 作为产物：
  描述：

  (1R,2R,6R,7R)-4,4-dimethyl-3,5,10-trioxatricyclo[5.2.1.02,6]decan-8-one 生成 (-)-2-<<(tert-butyl)dimethylsilyl>oxy>-5,6-exo-(isopropylidenedioxy)-7-oxabicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  JEGANATHAN, SURULIAPPA;VOGEL, PIERRE, J. ORG. CHEM., 56,(1991) N, C. 1139-1142

  摘要：

  DOI：

文献信息

• Total Synthesis ofL-Allose,L-Talose, and derivatives.
  作者：Yves Auberson、Pierre Vogel

  DOI：10.1002/hlca.19890720212

  日期：1989.3.15

  (1S, 4R, 5S, 6S)-5-exo, 6-exo-(Isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((−)-1) was transformed with high stereoselectivity to L-allose. Similarly, enantiomer (+)-1 was transformed into L-talose. The ketones (+)-1 and (−)-1 were derived from furan and 1-cyanovinyl (1S)-camphanate and 1-cyanovinyl (1R)-camphanate, respectively.

  将（1 S，4 R，5 S，6 S）-5- exo，6- exo-（异丙二烯二氧基）-7-氧杂双环[2.2.1]庚-2--2-（（-）- 1）转化为高对L-阿洛糖的立体选择性。类似地，对映异构体（+）- 1被转化为L-塔洛糖。酮（+1）-1和（-1）-1分别来自呋喃和1-氰基乙烯基（1S）-樟脑酸酯和1-氰基乙烯基（1R）-樟脑酸酯。
• 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。
• Enantiomerically pure 7-oxabicyclo[2.2.1]hept-5-en-2-yl derivatives (naked sugars) as synthetic intermediates. 18. Synthesis of .alpha.-(1.fwdarw.2)-, .alpha.-(1.fwdarw.3)-, .alpha.-(1.fwdarw.4)-, and .alpha.-(1.fwdarw.5)-C-linked disaccharides through 2,3,4,6-tetra-O-acetylglucopyranosyl radical additions to 3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one derivatives
  作者：R. Mampuya Bimwala、Pierre Vogel

  DOI：10.1021/jo00033a032

  日期：1992.3

  The ''naked sugar'' (+)-1 (1R,2S,4R)-2-cyano-7-oxabicyclo[2.2.1]hept-5-en-2-yl (1S')-camphanate) has been converted into (+)-(1R,4R,5R,6R)-3-methylidene-5-exo,6-exo(isopropylidenedioxy)-7-oxabicyclo[2.2.1]heptan-2-one ((+)-3) and (-)-(1S,4R,5R,6R)-5-exo-(benzeneselenyl)-6-endo-chloro-3-methylidene-7-oxabicyclo[2.2.1]heptan-2-one ((-)-26). Reductive addition of 2,3,4,6-tetra-O-acetylglucopyranosyl radical onto (+)-3 and (-)-26 were highly stereoselective giving exclusively 3-endo-(glucosylmethyl)-7-oxabicyclo[2.2.1]heptan-2-one derivatives. The anomeric selectivity (alpha-C-glucoside vs beta-C-glucoside) was 5.5:1 with (+)-3 and 8:1 with (-)-26. The C-glucosides so-obtained were transformed into alpha-(1 --> 2)-, alpha-(1 --> 3)-, alpha-(1 --> 4)-, and alpha-(1 --> 5)-C-linked disaccharide derivatives which combine alpha-D-glucopyranose with L-altro-hexonolactone, L-manno-hexonolactone, L-mannose, and L-(talo-hexofuranosid)uronic acid, respectively.
• 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
  作者：Suruliappa Jeganathan、Pierre Vogel

  DOI：10.1021/jo00003a041

  日期：1991.2

  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.
• AUBERSON, YVES;VOGEL, PIERRE, HELV. CHIM. ACTA, 72,(1989) N, C. 278-286
  作者：AUBERSON, YVES、VOGEL, PIERRE

  DOI：——

  日期：——