(R,R,R,R)-N(1)-benzyl-2-(hydroxymethyl)-3-benzyloxy-4,5-dihydroxypiperidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (R,R,R,R)-N(1)-benzyl-2-(hydroxymethyl)-3-benzyloxy-4,5-dihydroxypiperidine
• 英文别名: (+)-(3R,4R,5R,6R)-1-benzyl-5-(benzyloxy)-6-(hydroxymethyl)piperidine-3,4-diol；(3R,4R,5R,6R)-1-benzyl-6-(hydroxymethyl)-5-phenylmethoxypiperidine-3,4-diol
• 化学式: C₂₀H₂₅NO₄
• 分子量: 343.423
• InChiKey: KVAJXJHZGQOCAK-UAFMIMERSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  73.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (R,R,R,R)-N(1)-benzyl-2-(hydroxymethyl)-3-benzyloxy-4,5-dihydroxypiperidine 在 10 wt% Pd(OH)2 on carbon 、 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、506.66 kPa 条件下， 反应 48.0h， 以87%的产率得到1-脱氧甘露伊霉素
  参考文献：
  名称：

  Asymmetric Syntheses of (−)-1-Deoxymannojirimycin and (+)-1-Deoxyallonojirimycin via a Ring-Expansion Approach

  摘要：

  The asymmetric syntheses of (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin are described herein. The ring-closing iodoamination of two epimeric bishomoallylic amines to give the corresponding 5-iodomethylpyrrolidines was followed by in situ ring-expansion to give two diastereoisomerically pure (>99:1 dr) cyclic carbonates. Subsequent deprotection gave (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin as single diastereoisomers in 7.4 and 3.3% overall yield, respectively, from commercially available starting materials.

  DOI：

  10.1021/ol400735z
• 作为产物：
  描述：

  (R,R,R,R)-N(1)-benzyl-2-[(triisopropylsilyloxy)methyl]-3-benzyloxy-4,5-dihydroxypiperidine 在 吡啶 、 4-二甲氨基吡啶 、 potassium carbonate 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 38.0h， 生成 (R,R,R,R)-N(1)-benzyl-2-(hydroxymethyl)-3-benzyloxy-4,5-dihydroxypiperidine
  参考文献：
  名称：

  Asymmetric Syntheses of (−)-1-Deoxymannojirimycin and (+)-1-Deoxyallonojirimycin via a Ring-Expansion Approach

  摘要：

  The asymmetric syntheses of (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin are described herein. The ring-closing iodoamination of two epimeric bishomoallylic amines to give the corresponding 5-iodomethylpyrrolidines was followed by in situ ring-expansion to give two diastereoisomerically pure (>99:1 dr) cyclic carbonates. Subsequent deprotection gave (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin as single diastereoisomers in 7.4 and 3.3% overall yield, respectively, from commercially available starting materials.

  DOI：

  10.1021/ol400735z

文献信息

• Enantio- and Diastereoselective Syntheses of 3-Hydroxypiperidines through Iridium-Catalyzed Allylic Substitution
  作者：Johannes Hoecker、Georg C. Rudolf、Florian Bächle、Steffen Fleischer、Benjamin D. Lindner、Günter Helmchen

  DOI：10.1002/ejoc.201300445

  日期：2013.8

  Stereoselective syntheses of 3-hydroxypiperidines have been developed. Key intermediates are N-protected allylamines that are prepared by an enantioselective iridium-catalyzed allylic amination. A subsequent catch and release procedure that involves an epoxidation and base-mediated elimination yields δ-lactams that are suitably functionalized to prepare biologically active 3-hydroxypiperidines. In addition

  已经开发了 3-羟基哌啶的立体选择性合成。关键中间体是通过对映选择性铱催化的烯丙胺化反应制备的 N 保护的烯丙胺。随后的捕获和释放程序涉及环氧化和碱介导​​的消除，产生 δ-内酰胺，其被适当地官能化以制备具有生物活性的 3-羟基哌啶。此外，还描述了该方法在脱氧甘露野尻霉素、D-赤型鞘氨醇和对药物化学感兴趣的手性构件的全合成中的应用。
• Asymmetric syntheses of 2,5-dideoxy-2,5-imino-d-glucitol [(+)-DGDP] and 1,2,5-trideoxy-1-amino-2,5-imino-d-glucitol [(+)-ADGDP]
  作者：Stephen G. Davies、Aude L.A. Figuccia、Ai M. Fletcher、Paul M. Roberts、James E. Thomson

  DOI：10.1016/j.tet.2014.03.100

  日期：2014.6

  The asymmetric syntheses of 2,5-dideoxy-2,5-imino-D-glucitol [(+)-DGDP] and 1,2,5-trideoxy-1-amino-2,5-imino-D-glucitol [(+)-ADGDP] were achieved via the ring-closing iodoamination of an enantiopure bishomoallylic amine, followed by functionalisation of the resultant iodomethyl substituted pyrrolidine. In the case of (+)-DGDP, formation of the corresponding aziridinium ion followed by regioselective ring-opening with H2O gave the desired hydroxymethyl substituted pyrrolidine as a single diastereoisomer (>99:1 dr), with subsequent deprotection giving (+)-DGDP in good yield. Whereas in the case of (+)-ADGDP, displacement of iodide with NaN3 proved to be optimal, giving (+)-ADGDP in good yield after reduction and deprotection. (C) 2014 Elsevier Ltd. All rights reserved.
• Total synthesis of deoxymannojirimycin and d-mannolactam via carbonylation of 5-vinyloxazolidin-2-ones
  作者：Julian G Knight、Kirill Tchabanenko

  DOI：10.1016/s0040-4020(02)01534-x

  日期：2003.1

  The stereoselective synthesis of piperidine alkaloids deoxymannojirimycin and D-mannolactam. from D-serine has been achieved. The key step involves palladium-catalysed decarboxylative carbonylation of a serine-derived 5-vinyloxazolidin-2-one to give 6-(tert-butyldimethylsilyloxymethyl)-3,6-dihydro-1H-pyridin-2-one which was subsequently converted into the title compounds. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Asymmetric Syntheses of (−)-1-Deoxymannojirimycin and (+)-1-Deoxyallonojirimycin via a Ring-Expansion Approach
  作者：Stephen G. Davies、Aude L. A. Figuccia、Ai M. Fletcher、Paul M. Roberts、James E. Thomson

  DOI：10.1021/ol400735z

  日期：2013.4.19

  The asymmetric syntheses of (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin are described herein. The ring-closing iodoamination of two epimeric bishomoallylic amines to give the corresponding 5-iodomethylpyrrolidines was followed by in situ ring-expansion to give two diastereoisomerically pure (>99:1 dr) cyclic carbonates. Subsequent deprotection gave (-)-1-deoxymannojirimycin and (+)-1-deoxyallonojirimycin as single diastereoisomers in 7.4 and 3.3% overall yield, respectively, from commercially available starting materials.