(2R,3S,4R,5R,6R)-2-allyl-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)piperidine | 950599-08-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S,4R,5R,6R)-2-allyl-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)piperidine
• 英文别名: (2R,3R,4R,5S,6R)-3,4,5-tris(phenylmethoxy)-2-(phenylmethoxymethyl)-6-prop-2-enylpiperidine
• CAS: 950599-08-3
• 化学式: C₃₇H₄₁NO₄
• 分子量: 563.737
• InChiKey: FUUDCJQRROFRFU-KHKVHWIZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  42
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  49
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5R,6R)-2-allyl-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)piperidine 在 三氟甲磺酸三甲基硅酯 、 sodium hexamethyldisilazane 、 potassium hydrogencarbonate 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 42.58h， 生成
  参考文献：
  名称：

  Site-Selective Debenzylation of C-Allyl Iminosugars Enables Their Stereocontroled Structure Diversification at the C-2 Position

  摘要：

  A C-2 regioselective debenzylative cycloetherification/reductive elimination sequence applied to perbenzylated C-allyl iminosugars is described. This NIS/TMSOTf-triggered deprotection was successfully applied to five-, six-, and seven-membered C-allyl iminosugars including 1,2 cis and 1,2 trans stereoisomers. It allows rapid introduction of structural diversity at the key C-2 position in a stereoselective manner exploiting the anchimeric assistance of the intracyclic N-benzyl group, giving access to the 2-acetamido and 2-fluoro d-gluco configured C-allyl iminosugars and to the epimeric d-manno derivative.

  DOI：

  10.1021/acs.orglett.9b01712
• 作为产物：
  描述：

  N-benzyl-2,3,4,6-tetra-O-benzyl-D-glucopyranosylamine 在 ammonium cerium(IV) nitrate 、 4 A molecular sieve 、 三乙酰氧基硼氢化钠 、 溶剂黄146 、 sodium sulfate 、 二乙胺 、 N,N-二异丙基乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 1,2-二氯乙烷 、 乙腈 为溶剂， 反应 55.0h， 生成 (2R,3S,4R,5R,6R)-2-allyl-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)piperidine
  参考文献：
  名称：

  诺奇霉素C-糖苷的合成

  摘要：

  野尻霉素α- Ç -glycosides，其具有1-α-烯丙基-1-脱氧ñ -苄基-2,3,4,6-四Ö -benzylnojirimycin（9），作为进一步的关键中间体衍生化，已由市售产品合成 2,3,4,6-四-O-苄基-D-吡喃葡萄糖（3），通过它涉及治疗的高立体选择性过程3与苄胺，得到的葡糖胺4与烯丙基溴化镁 和 环化Fmoc-保护对伸长的开链氨基糖5的合成，氧化作用的游离羟基和分子内的还原胺化反应，在59％的总收率中可提供9％的收率。有效控制9的烯丙基附件需要N-脱苄基和环的Fmoc-保护氮。

  DOI：

  10.1039/b206623h

文献信息

• Synthesis and Evaluation of Lipophilic Aza-C-glycosides as Inhibitors of Glucosylceramide Metabolism
  作者：Tom Wennekes、Richard J. B. H. N. van den Berg、Thomas J. Boltje、Wilma E. Donker-Koopman、Bastiaan Kuijper、Gijsbert A. van der Marel、Anneke Strijland、Carlo P. Verhagen、Johannes M. F. G. Aerts、Herman S. Overkleeft

  DOI：10.1002/ejoc.200901208

  日期：2010.3

  The structure–activity relationship of lipophilic aza-C-glycosides as inhibitors of the three enzymes of glucosylceramide metabolism is investigated. A library of β-aza-C-glycosides was synthesized with variations in N-alkylation and the linker length/type to the lipophilic moiety. A cross-metathesis reaction was used to prepare a second library of α-aza-C-glycosides with D-gluco, L-ido and D-xylo

  研究了亲脂性氮杂-C-糖苷作为葡萄糖神经酰胺代谢三种酶抑制剂的构效关系。合成了一个 β-氮杂-C-糖苷库，其中 N-烷基化和亲脂性部分的接头长度/类型有所不同。使用交叉复分解反应制备第二个 α-氮杂-C-糖苷库，其中 D-葡萄糖、L-ido 和 D-木亚氨基糖核心具有类似的接头变异。对两个文库的评估均未发现葡萄糖神经酰胺合酶的有效或选择性抑制剂。然而，发现 β-aza-C-glycoside 43 是 β-glucosidase 2 的选择性抑制剂。葡萄糖脑苷脂酶的选择性抑制剂。
• Concise synthesis of bicyclic iminosugars <i>via</i> reductive functionalization of sugar-derived lactams and subsequent RCM reaction
  作者：Piotr Szcześniak、Bartłomiej Furman

  DOI：10.1039/d1ob01172c

  日期：——

  method for the synthesis of bicyclic iminosugars has been developed. The strategy is based on the partial reduction of sugar-derived lactams by Schwartz's reagent and tandem stereoselective nucleophile addition dictated by Woerpel's model which affords polyhydroxylated cyclic amines as key intermediates. Introduction of a vinyl or allyl group to the iminosugar produces diene derivatives that can be

  开发了一种合成双环亚氨基糖的有效方法。该策略基于通过 Schwartz 试剂和串联立体选择性亲核试剂加成的糖衍生内酰胺的部分还原，由 Woerpel 模型提供多羟基化环胺作为关键中间体。将乙烯基或烯丙基基团引入亚氨基糖产生二烯衍生物，该衍生物可以进行闭环复分解反应 (RCM)，以良好至极好的产率提供多羟基化吡咯里西啶、中氮茚和喹唑啉衍生物。该反应序列已应用于风信子 A 2的正式合成，它是一种多羟基化的吡咯里西啶生物碱。
• Sugar-derived cyclic imines: one-pot synthesis and direct functionalization
  作者：Piotr Szcześniak、Sebastian Stecko、Olga Staszewska-Krajewska、Bartłomiej Furman

  DOI：10.1016/j.tet.2014.01.039

  日期：2014.3

  A simple method for the synthesis of sugar-derived imines by a Schwartz's reagent reduction of easily available sugar lactams has been described. A direct addition of nucleophiles to the generated in situ cyclic imines and subsequent deprotection of hydroxyl function allows to convert sugar lactams in polyhydroxylated pyrrolidines and piperidines. (C) 2014 Elsevier Ltd. All rights
• Synthesis and biological evaluation of a small library of nojirimycin-derived bicyclic iminosugars
  作者：Laura Cipolla、Marcos Reis Fernandes、Maria Gregori、Cristina Airoldi、Francesco Nicotra

  DOI：10.1016/j.carres.2007.04.002

  日期：2007.9

  Novel nojirimycin-derived bicyclic structures, containing cyclic carbamate, urea and guanidine moieties have been synthesised starting from suitably protected alpha-C-vinylnojirimycin and alpha-C-allylnojirimycin, respectively, and their biological activity against different glycosidases and as antibacterial agents tested. (c) 2007 Elsevier Ltd. All rights reserved.
• Site-Selective Debenzylation of <i>C</i>-Allyl Iminosugars Enables Their Stereocontroled Structure Diversification at the C-2 Position
  作者：Quentin Foucart、Jérôme Marrot、Jérôme Désiré、Yves Blériot

  DOI：10.1021/acs.orglett.9b01712

  日期：2019.6.21

  A C-2 regioselective debenzylative cycloetherification/reductive elimination sequence applied to perbenzylated C-allyl iminosugars is described. This NIS/TMSOTf-triggered deprotection was successfully applied to five-, six-, and seven-membered C-allyl iminosugars including 1,2 cis and 1,2 trans stereoisomers. It allows rapid introduction of structural diversity at the key C-2 position in a stereoselective manner exploiting the anchimeric assistance of the intracyclic N-benzyl group, giving access to the 2-acetamido and 2-fluoro d-gluco configured C-allyl iminosugars and to the epimeric d-manno derivative.