2-(N-benzyloxycarbonyl)amino-6-O-methanesulfonyl-2,3,5-trideoxy-L-threo-hexono-1,4-lactone | 244793-55-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-(N-benzyloxycarbonyl)amino-6-O-methanesulfonyl-2,3,5-trideoxy-L-threo-hexono-1,4-lactone
• 英文别名: 2-[(2R,4R)-5-oxo-4-(phenylmethoxycarbonylamino)oxolan-2-yl]ethyl methanesulfonate
• CAS: 244793-55-3
• 化学式: C₁₅H₁₉NO₇S
• 分子量: 357.384
• InChiKey: CICSPLBQQVNVKF-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  116
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-(N-benzyloxycarbonyl)amino-6-O-methanesulfonyl-2,3,5-trideoxy-L-threo-hexono-1,4-lactone 在 palladium on activated charcoal 氢氧化钾 、 氢气 作用下， 以 水 、 乙酸乙酯 为溶剂， 反应 17.0h， 生成 (2R,4S)-(+)-4-Hydroxypipecolic acid
  参考文献：
  名称：

  从D-葡萄糖胺非对映选择性合成顺式-4-羟基哌酸。

  摘要：

  描述了一种快速合成顺式-4-羟基哌酸（1）的方法。关键步骤是从D-葡萄糖胺的三个高产率步骤中获得的2-乙酰氨基-6- O-乙酰基-2,3,5-三苯氧基-己-2-烯诺-1,4-内酯的非对映选择性加氢（3） 。通过分子内的C-2磺酸亲核取代C-6磺酸盐，可以从2-氨基-2,3,5-苯氧基-苏-己基-1,4-内酯衍生物形成哌啶环（10）。团体。

  DOI：

  10.1016/s0040-4020(01)80215-5
• 作为产物：
  描述：

  在 palladium on activated charcoal 吡啶 、 盐酸 、 sodium periodate 、 sodium azide 、 氢气 、 methyl orange 、 sodium cyanoborohydride 、 碳酸氢钠 、 对甲苯磺酸 、 copper(II) sulfate 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 76.0h， 生成 2-(N-benzyloxycarbonyl)amino-6-O-methanesulfonyl-2,3,5-trideoxy-L-threo-hexono-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

• Diastereoselective synthesis of cis-4-hydroxypipecolic acid from D-glucosamine.
  作者：Alejandro P. Nin、Oscar Varela、Rosa M. de Lederkremer

  DOI：10.1016/s0040-4020(01)80215-5

  日期：——

  An expeditious synthesis of cis-4-hydroxypipecolic acid (1) is described. The key step was diastereoselective hydrogenation of 2-acetamido-6-O-acetyl-2,3,5-trideoxy-hex-2-enono-1,4-lactone (3), obtained in three high yielding steps from D-glucosamine. The formation of the piperidine ring from 2-amino-2,3,5-trideoxy-threo-hexono-1,4-lactone derivative (10) was achieved by intramolecular nucleophilic

  描述了一种快速合成顺式-4-羟基哌酸（1）的方法。关键步骤是从D-葡萄糖胺的三个高产率步骤中获得的2-乙酰氨基-6- O-乙酰基-2,3,5-三苯氧基-己-2-烯诺-1,4-内酯的非对映选择性加氢（3） 。通过分子内的C-2磺酸亲核取代C-6磺酸盐，可以从2-氨基-2,3,5-苯氧基-苏-己基-1,4-内酯衍生物形成哌啶环（10）。团体。
• 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.