6,7-O-cyclohexylidene-3,5-dideoxy-D-arabino-heptono-1,4-lactone | 244633-55-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,7-O-cyclohexylidene-3,5-dideoxy-D-arabino-heptono-1,4-lactone
• 英文别名: (3S,5S)-5-[[(3S)-1,4-dioxaspiro[4.5]decan-3-yl]methyl]-3-hydroxyoxolan-2-one
• CAS: 244633-55-4
• 化学式: C₁₃H₂₀O₅
• 分子量: 256.299
• InChiKey: NHIDNVOADPWHHG-VWYCJHECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  6,7-O-cyclohexylidene-3,5-dideoxy-D-arabino-heptono-1,4-lactone 在 palladium on activated charcoal 吡啶 、 盐酸 、 氢氧化钾 、 sodium periodate 、 sodium azide 、 氢气 、 methyl orange 、 sodium cyanoborohydride 、 碳酸氢钠 、 对甲苯磺酰氯 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 80.5h， 生成 (2S,4r)-顺式-4-羟基哌啶-2-羧酸
  参考文献：
  名称：

  Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from d-Glucoheptono-1,4-lactone

  摘要：

  Enantiomerically pure (2R,4S)-4-hydroxypipecolic acid [(+)-1] was synthesized from D-glucoheptono-1,4-lactone (2) via the 3,5-dideoxy-D-xylo-heptono-1,4-lactone (7). The latter was readily prepared by benzoylation of 2, followed by p-elimination and diastereoselective hydrogenation of the resulting furanones (4). Compound 7 was converted into the 6,7-O-eyclohexylidene derivative 11, which on treatment with tosyl chloride for long periods afforded the 2-chloro derivative 14, the precursor of the azide 15. Hydrogenolysis of 15 and protection of the amine gave the N-benzyloxycarbonyl derivative 19, having the required configuration for the stereocenters at C-2 and C-4. Removal of the cyclohexylidene group by hydrolysis and subsequent oxidative degradation of the resulting glycol system afforded the hexurono-6,3-lactone 21 as a key intermediate. Chemoselective reduction of the aldehyde function of 21 led to the alcohol 23, which was derivatized as the mesylate 24. Releasing of the amino group by hydrogenation, and dissolution of resulting 25 in aqueous alkali, promoted the intramolecular nucleophilic displacement of the mesylate to give (+)-1. Its enantiomer [(-)-1] was prepared by a similar sequence starting from 2.

  DOI：

  10.1021/jo990445+
• 作为产物：
  描述：

  环己酮 、 在 对甲苯磺酸 、 copper(II) sulfate 作用下， 反应 20.0h， 以35%的产率得到6,7-O-cyclohexylidene-3,5-dideoxy-D-arabino-heptono-1,4-lactone
  参考文献：
  名称：

  Enantioselective Synthesis of (2R,4S)- and (2S,4R)-4-Hydroxypipecolic Acid from d-Glucoheptono-1,4-lactone

  摘要：

  Enantiomerically pure (2R,4S)-4-hydroxypipecolic acid [(+)-1] was synthesized from D-glucoheptono-1,4-lactone (2) via the 3,5-dideoxy-D-xylo-heptono-1,4-lactone (7). The latter was readily prepared by benzoylation of 2, followed by p-elimination and diastereoselective hydrogenation of the resulting furanones (4). Compound 7 was converted into the 6,7-O-eyclohexylidene derivative 11, which on treatment with tosyl chloride for long periods afforded the 2-chloro derivative 14, the precursor of the azide 15. Hydrogenolysis of 15 and protection of the amine gave the N-benzyloxycarbonyl derivative 19, having the required configuration for the stereocenters at C-2 and C-4. Removal of the cyclohexylidene group by hydrolysis and subsequent oxidative degradation of the resulting glycol system afforded the hexurono-6,3-lactone 21 as a key intermediate. Chemoselective reduction of the aldehyde function of 21 led to the alcohol 23, which was derivatized as the mesylate 24. Releasing of the amino group by hydrogenation, and dissolution of resulting 25 in aqueous alkali, promoted the intramolecular nucleophilic displacement of the mesylate to give (+)-1. Its enantiomer [(-)-1] was prepared by a similar sequence starting from 2.

  DOI：

  10.1021/jo990445+

文献信息

• Enantioselective Synthesis of (2<i>R</i>,4<i>S</i>)- and (2<i>S</i>,4<i>R</i>)-4-Hydroxypipecolic Acid from <scp>d</scp>-Glucoheptono-1,4-lactone
  作者：Christián Di Nardo、Oscar Varela

  DOI：10.1021/jo990445+

  日期：1999.8.1

  Enantiomerically pure (2R,4S)-4-hydroxypipecolic acid [(+)-1] was synthesized from D-glucoheptono-1,4-lactone (2) via the 3,5-dideoxy-D-xylo-heptono-1,4-lactone (7). The latter was readily prepared by benzoylation of 2, followed by p-elimination and diastereoselective hydrogenation of the resulting furanones (4). Compound 7 was converted into the 6,7-O-eyclohexylidene derivative 11, which on treatment with tosyl chloride for long periods afforded the 2-chloro derivative 14, the precursor of the azide 15. Hydrogenolysis of 15 and protection of the amine gave the N-benzyloxycarbonyl derivative 19, having the required configuration for the stereocenters at C-2 and C-4. Removal of the cyclohexylidene group by hydrolysis and subsequent oxidative degradation of the resulting glycol system afforded the hexurono-6,3-lactone 21 as a key intermediate. Chemoselective reduction of the aldehyde function of 21 led to the alcohol 23, which was derivatized as the mesylate 24. Releasing of the amino group by hydrogenation, and dissolution of resulting 25 in aqueous alkali, promoted the intramolecular nucleophilic displacement of the mesylate to give (+)-1. Its enantiomer [(-)-1] was prepared by a similar sequence starting from 2.