(6R)-3-O-(tert-Butyldimethylsilyl)-6-C-<(1'R,3'S,4'R,5'S,6'S)-6'-endo-chloro-5'-endo-(methoxymethoxy)-2'-oxo-7'-oxabicyclo<2.2.1>hept-3'-exo-yl>-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranose | 170873-15-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (6R)-3-O-(tert-Butyldimethylsilyl)-6-C-<(1'R,3'S,4'R,5'S,6'S)-6'-endo-chloro-5'-endo-(methoxymethoxy)-2'-oxo-7'-oxabicyclo<2.2.1>hept-3'-exo-yl>-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranose
• 英文别名: (1S,3S,4R,5S,6S)-3-[(1R)-2-[(3aR,5R,6S,6aR)-6-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-5-yl]-1-hydroxyethyl]-6-chloro-5-(methoxymethoxy)-7-oxabicyclo[2.2.1]heptan-2-one
• CAS: 170873-15-1
• 化学式: C₂₃H₃₉ClO₉Si
• 分子量: 523.096
• InChiKey: WGLZJUUANBNTIH-XWBHFLBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (6R)-3-O-(tert-Butyldimethylsilyl)-6-C-<(1'R,3'S,4'R,5'S,6'S)-6'-endo-chloro-5'-endo-(methoxymethoxy)-2'-oxo-7'-oxabicyclo<2.2.1>hept-3'-exo-yl>-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranose 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 18.0h， 以89%的产率得到(6R)-3-O-(tert-Butyldimethylsilyl)-6-C-<(1'S,4'S,5'R,6'S,7'S)-7'-endo-chloro-6'-endo-(methoxymethoxy)-3'-oxo-2',8'-dioxabicyclo<3.2.1>oct-4'-exo-yl>-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranose
  参考文献：
  名称：

  Synthesis of Undeculofuranoside Derivatives of the Herbicidins and of Analogs

  摘要：

  The condensation of 3-O-(tert-butyldimethylsilyl)-5-deoxy-1,2-O-isopropylidene-alpha-D-xylo-hexodialdo-1,4-furanose (obtained in six steps (35%) from D-glucurono-6,3-lactone) with the lithium enolate of (+/-)6-endo-chloro-5-endo-(methoxymethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (derived in six steps (25%) from the Diels-Alder adduct of furan to 1-cyanovinyl acetate) was highly exo face selective giving two major aldols that were separated readily. One of them was converted to 6,10-anhydro-5-deoxy-1,2-O-isopropylidene-9-O-(methoymethyl)-alpha-D-arabino-L-ido-7-undeculofuranose-(1,4)-pyranose-(7,3), a semiprotected form of the long-chain carbohydrate moiety of the herbicidins. The synthesis implies the acid-promoted isomerization of 10,11-anhydro-5,7-dideoxy-1,2-O-isopropylidene-9-O-(methoxymethyl)-7-C-[(2-nitrophenyl)selenomethyl]-beta-L-ido-L-ido-undecofuranose.

  DOI：

  10.1021/jo00123a021
• 作为产物：
  描述：

  D-glucurono-3,6-lactone acetonide 在 吡啶 、 2,6-二甲基吡啶 、 正丁基锂 、 偶氮二异丁腈 、 三正丁基氢锡 、 二异丁基氢化铝 、 sodium cyanoborohydride 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 13.17h， 生成 (6R)-3-O-(tert-Butyldimethylsilyl)-6-C-<(1'R,3'S,4'R,5'S,6'S)-6'-endo-chloro-5'-endo-(methoxymethoxy)-2'-oxo-7'-oxabicyclo<2.2.1>hept-3'-exo-yl>-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuranose
  参考文献：
  名称：

  Synthesis of Undeculofuranoside Derivatives of the Herbicidins and of Analogs

  摘要：

  The condensation of 3-O-(tert-butyldimethylsilyl)-5-deoxy-1,2-O-isopropylidene-alpha-D-xylo-hexodialdo-1,4-furanose (obtained in six steps (35%) from D-glucurono-6,3-lactone) with the lithium enolate of (+/-)6-endo-chloro-5-endo-(methoxymethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (derived in six steps (25%) from the Diels-Alder adduct of furan to 1-cyanovinyl acetate) was highly exo face selective giving two major aldols that were separated readily. One of them was converted to 6,10-anhydro-5-deoxy-1,2-O-isopropylidene-9-O-(methoymethyl)-alpha-D-arabino-L-ido-7-undeculofuranose-(1,4)-pyranose-(7,3), a semiprotected form of the long-chain carbohydrate moiety of the herbicidins. The synthesis implies the acid-promoted isomerization of 10,11-anhydro-5,7-dideoxy-1,2-O-isopropylidene-9-O-(methoxymethyl)-7-C-[(2-nitrophenyl)selenomethyl]-beta-L-ido-L-ido-undecofuranose.

  DOI：

  10.1021/jo00123a021

文献信息

• Synthesis of Undeculofuranoside Derivatives of the Herbicidins and of Analogs
  作者：Fabienne Emery、Pierre Vogel

  DOI：10.1021/jo00123a021

  日期：1995.9

  The condensation of 3-O-(tert-butyldimethylsilyl)-5-deoxy-1,2-O-isopropylidene-alpha-D-xylo-hexodialdo-1,4-furanose (obtained in six steps (35%) from D-glucurono-6,3-lactone) with the lithium enolate of (+/-)6-endo-chloro-5-endo-(methoxymethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (derived in six steps (25%) from the Diels-Alder adduct of furan to 1-cyanovinyl acetate) was highly exo face selective giving two major aldols that were separated readily. One of them was converted to 6,10-anhydro-5-deoxy-1,2-O-isopropylidene-9-O-(methoymethyl)-alpha-D-arabino-L-ido-7-undeculofuranose-(1,4)-pyranose-(7,3), a semiprotected form of the long-chain carbohydrate moiety of the herbicidins. The synthesis implies the acid-promoted isomerization of 10,11-anhydro-5,7-dideoxy-1,2-O-isopropylidene-9-O-(methoxymethyl)-7-C-[(2-nitrophenyl)selenomethyl]-beta-L-ido-L-ido-undecofuranose.