(2S,3R,4R)-2,3,5-tri-O-benzyl-4-O-formyl-pentanal | 155931-84-3

• 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: (2S,3R,4R)-2,3,5-tri-O-benzyl-4-O-formyl-pentanal
• 英文别名: 2,3,5-tri-O-benzyl-4-O-formyl-D-arabinose；[(2R,3R,4S)-5-oxo-1,3,4-tris(phenylmethoxy)pentan-2-yl] formate
• CAS: 155931-84-3
• 化学式: C₂₇H₂₈O₆
• 分子量: 448.516
• InChiKey: PQDVQEJQAUJKES-PFBJBMPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  33
• 可旋转键数：
  15
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2S,3R,4R)-2,3,5-tri-O-benzyl-4-O-formyl-pentanal 在 titanium(IV) isopropylate 、 sodium hexamethyldisilazane 、 (R)-3,3'-diiodo-[1,1'-binaphthalene]-2,2'-diol 、 Cinchonidine 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 33.5h， 生成 (2R,3S,4S,5S,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-methoxy-2-oxido-1,2-oxaphosphinan-3yl acetate
  参考文献：
  名称：

  六元环状 P-手性亚膦酸铵-硼烷的合成、表征和偶联反应；用于糖模拟物立体选择性合成的反应性 H-次膦酸盐等价物

  摘要：

  葡萄糖和甘露糖系列中 P-手性亚膦酸铵-硼烷配合物的立体选择性合成已从 P(V) 膦衍生物发展而来。已经研究了这些光酮供体与醇的偶联反应，特别强调保护基团和条件对立体选择性的影响。亚膦酸酯-硼烷复合物可直接用于偶联反应，产物原位氧化以得到二糖的磷酮模拟物。在这些研究的基础上，建立了合成 β-葡萄糖和 α- 和 β- 甘露糖构型伯醇的成功方案。二聚体化合物的去保护导致了新的α-或β-(1→6)-连接的糖模拟物家族。

  DOI：

  10.1021/ja305104b
• 作为产物：
  描述：

  3,4,6-三苄氧基-D-葡萄烯糖 在 sodium periodate 、 四氧化锇 作用下， 以 乙醚 、 水 为溶剂， 反应 6.0h， 以64%的产率得到(2S,3R,4R)-2,3,5-tri-O-benzyl-4-O-formyl-pentanal
  参考文献：
  名称：

  六元环状 P-手性亚膦酸铵-硼烷的合成、表征和偶联反应；用于糖模拟物立体选择性合成的反应性 H-次膦酸盐等价物

  摘要：

  葡萄糖和甘露糖系列中 P-手性亚膦酸铵-硼烷配合物的立体选择性合成已从 P(V) 膦衍生物发展而来。已经研究了这些光酮供体与醇的偶联反应，特别强调保护基团和条件对立体选择性的影响。亚膦酸酯-硼烷复合物可直接用于偶联反应，产物原位氧化以得到二糖的磷酮模拟物。在这些研究的基础上，建立了合成 β-葡萄糖和 α- 和 β- 甘露糖构型伯醇的成功方案。二聚体化合物的去保护导致了新的α-或β-(1→6)-连接的糖模拟物家族。

  DOI：

  10.1021/ja305104b

文献信息

• H-Phosphonylphosphonate triethylester: the first member of a novel family of stable bisphosphorylated compounds; its short synthesis and reactivity with aldehydes
  作者：Philippe Bisseret、Jacques Eustache

  DOI：10.1016/s0040-4039(01)01798-1

  日期：2001.11

  A short preparation of the first member (1) of the novel H-phosphonylphosphonate family is described. Its reaction with aldehydes provides a straightforward access to the hitherto almost unprecedented class of α-hydroxyphosphinylphosphonates 3 of potential value in particular in medicinal chemistry.

  描述了新的H-膦酰基膦酸酯家族的第一成员（1）的简短制备。其与醛的反应可直接获得迄今为止几乎前所未有的一类具有潜在价值的α-羟基次膦酰基膦酸酯3，特别是在药物化学中。
• Synthesis of di- and trihydroxy proline derivatives from D-glycals: Application in the synthesis of polysubstituted pyrrolizidines and bioactive 1C-aryl/alkyl pyrrolidines
  作者：Ashish Kumar Verma、Sateesh Dubbu、Ande Chennaiah、Yashwant D. Vankar

  DOI：10.1016/j.carres.2019.02.004

  日期：2019.3

  O-benzyl protected proline derivatives have been synthesized from D-glycals and 2C-formyl-glycals. One of the di-O-benzyl protected proline derivatives has been utilized for the synthesis of polysubstituted pyrrolizidines via [3 + 2] cycloaddition in a stereoselective manner. Further, we also report on the stereoselective synthesis of biologically active 1C-aryl/alkyl pyrrolidines i.e. 4-epi-radicamine

  从D-糖和2C-甲酰基-糖合成了六种不同类型的O-苄基保护的脯氨酸衍生物。一种二-O-苄基保护的脯氨酸衍生物已被用于通过立体选择性方式通过[3 + 2]环加成反应合成多取代的吡咯并核苷。此外，我们还报告了通过多种D的双重还原胺化反应，对具有生物活性的1C-芳基/烷基吡咯烷（即4-上消旋胺B，4-上消旋胺A，1C丁基和1C-甲基吡咯烷）进行立体选择性合成的报道。 -葡萄糖衍生的二酮与对甲氧基苄胺。
• Cyclic Phosphonate Analogs of Hexopyranoses
  作者：James W. Darrow、Dale G. Drueckhammer

  DOI：10.1021/jo00090a014

  日期：1994.6

  Acyclic and cyclic analogs of D-glucopyranose and D-mannopyranose have been prepared in which the anomeric carbon has been replaced with a phosphorus. Base-catalyzed addition of dimethyl phosphite to di-O-isopropylidene-D-arabinose followed by recrystallization yields only the acyclic gluco-isomer, through what appears to be a selective recrystallization process. The use of diethyl phosphite under similar conditions yielded only the acyclic manno-isomer. The stereochemistry of each was ascertained through comparison of the pentaacetylated derivatives 11 and 12. For the cyclic analogs 1 and 2, synthesis consists of acid-catalyzed trimethyl phosphite addition to the carbonyl of a hydroxyl-protected open-chain D-arabinose derivative, removal of a formate ester from the 4-hydroxyl group, and base-catalyzed transesterification/cyclization. All four possible cyclic alpha-hydroxy phosphonate diastereomers were synthesized in roughly equal amounts. Complete separation of the gluco- and manno-isomers was accomplished, and Homonuclear two-dimensional J-spectroscopy was used to supplement-standard NMR analysis in order to completely characterize the isolated diastereomers 21 and 22 and assign gluco- and manno-stereochemistry, respectively.
• Preparation of <i>C</i>-1 Glycals via Olefin Metathesis. A Convergent and Flexible Approach to <i>C</i>-Glycoside Synthesis¹
  作者：Daniel Calimente、Maarten H. D. Postema

  DOI：10.1021/jo982331o

  日期：1999.3.1
• Alternative Synthesis of P-Chiral Phosphonite-Borane Complexes: Application to the Synthesis of Phostone–Phostone Dimers
  作者：Angélique Ferry、Gaëlle Malik、Pascal Retailleau、Xavier Guinchard、David Crich

  DOI：10.1021/jo400864s

  日期：2013.7.19

  An improved strategy for the synthesis of P-chiral gluco- and manno-phosphonite-borane complexes is described on the basis of the addition of diethyl phosphonite-borane to a glucal-derived aldehyde, followed by a cyclization coupled with an ethyl/methyl exchange. This direct P(III) strategy facilitates the obtention of various P-chiral phosphonite-boranes, of which further coupling reactions are described leading to the selective synthesis of two phostone dimers.