(5S,6R)-5-(tert-butyldimethylsilanyloxy)-6-(tert-butyldimethylsilanyloxymethyl)-5,6-dihydropyran-2-one | 186257-42-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (5S,6R)-5-(tert-butyldimethylsilanyloxy)-6-(tert-butyldimethylsilanyloxymethyl)-5,6-dihydropyran-2-one
• 英文别名: 4,6-di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-D-erythro-hex-2-eno-1,5-lactone；(2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3-dihydropyran-6-one
• CAS: 186257-42-1
• 化学式: C₁₈H₃₆O₄Si₂
• 分子量: 372.652
• InChiKey: VZBWOTWMTJWBOZ-LSDHHAIUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.88
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (5S,6R)-5-(tert-butyldimethylsilanyloxy)-6-(tert-butyldimethylsilanyloxymethyl)-5,6-dihydropyran-2-one 在 18-冠醚-6 、 benzenesulfinic acid sodium salt 、 phenylsulfonylpropa-1,2-diene 作用下， 以 四氢呋喃 为溶剂， 反应 240.0h， 以11%的产率得到(5S,6R)-5-((tert-butyldimethylsilyl)oxy)-6-(hydroxymethyl)-5,6-dihydro-2H-pyran-2-one
  参考文献：
  名称：

  d-葡萄糖经Padwa烯基砜[3 + 2]-阴离子环加成消除从d-葡萄糖合成（-）-棘孢菌素的立体控制合成路线

  摘要：

  （ - ） -的一种新形式的全合成echinosporin已经开发基于Padwa [3 + 2] allenylsulfone的-cycloadditive消去反应4与d葡萄糖衍生的烯酮14，其提供环加成12。

  DOI：

  10.1021/ol301090v
• 作为产物：
  描述：

  3,4,6-tri-O-tert-butyldimethylsilyl-2-deoxy-D-arabino-hexono-1,5-lactone 在 正丁基锂 、 2-三甲基硅基-1,3-二噻吩 作用下， 生成 (5S,6R)-5-(tert-butyldimethylsilanyloxy)-6-(tert-butyldimethylsilanyloxymethyl)-5,6-dihydropyran-2-one
  参考文献：
  名称：

  基于糖内酯的霍纳-埃蒙斯和彼得森反应，合成甲基3-脱氧-醛糖醛酸甲酯及其2-脱氧异构体的途径

  摘要：

  将两种试剂：2-三甲基甲硅烷基-和2- [双（2,2,2-三氟乙氧基）磷酰基] -1,3-二硫杂环丁烷用于从异构的2-脱氧六邻体-1构建合适的乙烯酮硫缩醛，通过霍纳-埃蒙斯或彼得森反应生成5-内酯。结果的比较表明，第二种试剂更有前景，因为它形成了所需的烯酮硫缩醛作为唯一产物。使用NBS / MeOH在CH 2 Cl 2中，通过氧化水解反应将后者直接立体选择性转化为标题αulosonates 。2-脱氧-磺基甲酸甲酯的构建涉及先前通过LiBH 4 -TMSCl物种对双键的氢化，以及随后在THF水溶液中用NBS水解。

  DOI：

  10.1016/s0040-4020(99)00049-6

文献信息

• Enantioselective synthesis of 5-substituted α,β-unsaturated δ-lactones: application to the synthesis of styryllactones
  作者：Joel M Harris、George A O’Doherty

  DOI：10.1016/s0040-4039(99)02050-x

  日期：2000.1

  A flexible enantioselective synthesis of highly functionalized 5-substituted α,β-unsaturated δ-lactones has been achieved by applying the Sharpless catalytic asymmetric dihydroxylation to vinylfuran as the key step. The resulting diols are produced in high enantio excess and can be stereoselectively transformed into differentially protected δ-lactones through a short reaction sequence.

  通过对乙烯基呋喃进行Sharpless催化不对称二羟基化反应作为关键步骤，已经实现了高度官能化的5个取代的α，β-不饱和δ-内酯的柔性对映选择性合成。所产生的二醇以高对映体过量产生，并且可以通过短的反应序列立体选择性地转化为差异保护的δ-内酯。
• Synthesis, structure and chiroptical properties of isoxazolidin-5-ones
  作者：Jadwiga Frelek、Irma Panfil、Przemyslaw Gluzinski、Marek Chmielewski

  DOI：10.1016/s0957-4166(96)00449-1

  日期：1996.12

  Several isoxazolidin-5-ones were synthesized in an addition - rearrangement reaction from corresponding sugar lactones and hydroxylamines. The sign of the Cotton effect at ca. 220 nm can be correlated to the absolute configuration of the stereogenic center at C3 and can be predicted by Weigang's sector rule. X-ray diffraction study performed for 11 and 12 confirms the configuration at C3 to be 3S and 3R, respectively. Copyright (C) 1996 Elsevier Science Ltd
• Syntheses of four d- and l-hexoses via diastereoselective and enantioselective dihydroxylation reactions
  作者：Joel M. Harris、Mark D. Keränen、Hang Nguyen、Victor G. Young、George A. O'Doherty

  DOI：10.1016/s0008-6215(00)00031-8

  日期：2000.8

  An expeditious approach to various protected hexoses has been developed by the use of the Sharpless catalytic asymmetric dihydroxylation reaction. Applying the Sharpless catalytic asymmetric dihydroxylation reaction on vinylfuran, diols with high enantioexcess are produced. The resulting diols call be stereoselectively transformed into either protected D- or L-mannose in five steps and approximately 39% yield from furfural. Similarly, both D- and L-talose and gulose have been synthesized in 19% overall yields, respectively. Using a modified strategy, both protected D- and L-gulo- and allo-sugar-delta-lactones were synthesized in eight steps and similar to 20% overall yield from furfural. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Configurational Assignment of 5-Substituted Pyrazolidin-3-ones Using Circular Dichroism Spectroscopy
  作者：Jadwiga Frelek、Irma Panfil、Zofia Urbańczyk-Lipkowska、Marek Chmielewski

  DOI：10.1021/jo9803232

  日期：1999.8.1

  The chiroptical properties of the title compounds bearing various substituents at the N(1) and N(2) nitrogen atoms are discussed. It was found that the sign of the n-pi* Cotton effect centered at about the 230-250 nm region can be correlated with the absolute configuration of the stereogenic center at C(5). It was also found that the sign of this Cotton effect is predictable by Weigang's lactam sector rule. MNIX calculations, supported by X-ray measurements, showed that substituents at the nitrogen atoms significantly affect the conformation of the five-membered ring. It was additionally concluded that the conformation of the five-membered ring in 5-substituted pyrazolidin-3-ones is the sign-determining factor for an n-pi* transition.