(R,R,R,R)-N(1)-benzyl-2-[(triisopropylsilyloxy)methyl]-3-benzyloxy-4,5-dihydroxy-4,5-O-carbonylpiperidine | 1429412-96-3

• 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-[(triisopropylsilyloxy)methyl]-3-benzyloxy-4,5-dihydroxy-4,5-O-carbonylpiperidine
• 英文别名: (3aR,6R,7R,7aR)-5-benzyl-7-phenylmethoxy-6-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyridin-2-one
• CAS: 1429412-96-3
• 化学式: C₃₀H₄₃NO₅Si
• 分子量: 525.761
• InChiKey: GLKZQBMOLVOAAR-CXDXLJMYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.55
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  57.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (R,R,R,R)-N(1)-benzyl-2-[(triisopropylsilyloxy)methyl]-3-benzyloxy-4,5-dihydroxy-4,5-O-carbonylpiperidine 在 吡啶 、 4-二甲氨基吡啶 、 10 wt% Pd(OH)2 on carbon 、 氢气 、 potassium carbonate 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 20.0 ℃ 、506.66 kPa 条件下， 反应 102.0h， 生成 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-hydroxy-5-(iodomethyl)pyrrolidine 在 silver tetrafluoroborate 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 17.0h， 生成 (R,R,R,R)-N(1)-benzyl-2-[(triisopropylsilyloxy)methyl]-3-benzyloxy-4,5-dihydroxy-4,5-O-carbonylpiperidine
  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

• Asymmetric Syntheses of (−)-ADMJ and (+)-ADANJ: 2-Deoxy-2-amino Analogues of (−)-1-Deoxymannojirimycin and (+)-1-Deoxyallonojirimycin
  作者：Stephen G. Davies、Aude L. A. Figuccia、Ai M. Fletcher Paul、M. Roberts、James E. Thomson

  DOI：10.1021/acs.joc.6b01107

  日期：2016.8.5

  ring-opening of the corresponding aziridinium intermediates with a tethered carbamate moiety) to give oxazolidin-2-ones was initially optimized on a model system. Subsequent application of this methodology to two enantiopure bishomoallylic amines (which were produced via aminohydroxylation of an α,β-unsaturated ester, partial reduction, and reaction of the corresponding aldehyde with vinylmagnesium bromide)

  本文描述了（-）-ADMJ和（+）-ADANJ，（-）-1-脱氧甘露糖霉素和（+）-1-脱氧烯隆吉利霉素的2-脱氧-2-氨基类似物的不对称合成。首先在模型系统上优化了用于将双烯丙基烯丙基胺进行闭环碘化胺化，然后进行原位扩环（通过分子连接的带有环氨基甲酸酯部分的叠氮基中间体的分子内开环）的方法，以得到恶唑烷定-2-酮。这种方法的后续应用两个对映体纯的胺bishomoallylic（其分别通过α，β不饱和酯，部分还原，并用乙烯基溴化镁相应的醛的反应的氨羟化生产）也进行伴随Ñ-进行脱苄基作用，得到相应的非对映异构纯的（> 99：1 dr）恶唑烷二-2-酮。随后对这些对映体纯模板进行脱保护，分别得到（-）-ADMJ和（+）-ADANJ作为单一非对映异构体，总收率分别为16％和24％。
• 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.