(±)-cis-6-((tert-butyldimethylsilyl)oxy)-3,6-dihydro-2H-pyran-3-ol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (±)-cis-6-((tert-butyldimethylsilyl)oxy)-3,6-dihydro-2H-pyran-3-ol
• 英文别名: cis-(±)-6-((tert-butyldimethylsilyl)oxy)-3,6-dihydro-2H-pyran-3-ol；cis-(±)-6-[(tert-butyldimethylsilyl)oxy]-3,6-dihydro-2H-pyran-3-ol；cis-(+/-)-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-ol；(3S,6R)-6-[tert-butyl(dimethyl)silyl]oxy-3,6-dihydro-2H-pyran-3-ol
• 化学式: C₁₁H₂₂O₃Si
• 分子量: 230.379
• InChiKey: XXLQTOLVNZXFAX-VHSXEESVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (±)-cis-6-((tert-butyldimethylsilyl)oxy)-3,6-dihydro-2H-pyran-3-ol 在 lipase AK 、 4 A molecular sieve 作用下， 以 phosphate buffer 、 丙酮 为溶剂， 反应 108.0h， 生成 (3R,6R)-cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetate
  参考文献：
  名称：

  Efficient and practical synthesis of both enantiomers of 6-silyloxy-3-pyranone derivatives

  摘要：

  Lipase catalyzed kinetic resolution of racemic cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-ol (rac)-1 was achieved in high enantiomeric excess. Transesterification of (rac)-1 with vinylacetate in 'BuOMe yielded the alcohol (3S,6R)-1 in 99.0% ee, whereas (3R,6S)-1 was obtained, in 99.0% ee, by the lipase catalyzed ester hydrolysis of acetate (3R,6S)-2, which was obtained along with the transesterification. Both (3S,6R)-1 and (3R,6S)-1 were subjected to oxidation to provide the corresponding 6-silyloxy-3-pyranone (6R)-3 and (6S)-3, respectively. Application to the synthesis of 7, which is the key intermediate of asymmetric synthesis of pseudomonic acid A 9 is also described. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00424-9
• 作为产物：
  描述：

  2,6-二氢-6-羟基-3(3H)-吡喃酮 在 吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride heptahydrate 、 silver nitrate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.83h， 生成 (±)-cis-6-((tert-butyldimethylsilyl)oxy)-3,6-dihydro-2H-pyran-3-ol
  参考文献：
  名称：

  Pd催化的二氢吡喃烯丙基烷基化级联反应：呋喃并[3,2- c ]吡喃的区域选择性合成

  摘要：

  区域选择性钯催化的烯丙基烷基化级联反应由各种环状β-二羰基双亲核试剂和3,6-二氢-2 H-吡喃双亲电试剂形成呋喃[3,2- c ]吡喃。二氢吡喃底物中的烯丙基碳酸酯和异头甲硅烷氧基离去基团的组合允许控制该反应中许多区域化学的可能性。环合进行立体会聚，以从顺式或反式取代的起始原料产生顺式融合的呋喃吡喃。

  DOI：

  10.1021/ol400902d

文献信息

• Pd-Catalyzed Allylic Alkylation Cascade with Dihydropyrans: Regioselective Synthesis of Furo[3,2-<i>c</i>]pyrans
  作者：Mark J. Bartlett、Claire A. Turner、Joanne E. Harvey

  DOI：10.1021/ol400902d

  日期：2013.5.17

  A regioselective palladium-catalyzed allylic alkylation cascade forms furo[3,2-c]pyrans from various cyclic β-dicarbonyl bis-nucleophiles and 3,6-dihydro-2H-pyran bis-electrophiles. The combination of allylic carbonate and anomeric siloxy leaving groups in the dihydropyran substrate allows control of the many regiochemical possibilities in this reaction. Annulation proceeds stereoconvergently to give

  区域选择性钯催化的烯丙基烷基化级联反应由各种环状β-二羰基双亲核试剂和3,6-二氢-2 H-吡喃双亲电试剂形成呋喃[3,2- c ]吡喃。二氢吡喃底物中的烯丙基碳酸酯和异头甲硅烷氧基离去基团的组合允许控制该反应中许多区域化学的可能性。环合进行立体会聚，以从顺式或反式取代的起始原料产生顺式融合的呋喃吡喃。
• Stereoselective nucleophilic substitution of 6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetate: application to the synthesis of a NK1 receptor antagonist
  作者：Kazutoshi Sugawara、Tomiki Hashiyama

  DOI：10.1016/j.tetlet.2007.03.104

  日期：2007.5

  Reaction of chiral cis- and trans-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-yl acetates with various nucleophiles (allyltrimethylsilane, bistrimethylsilylacetylene, benzyl alcohol, benzyl carbamate etc.) in the presence of a Lewis acid gave the corresponding 2,3-unsaturated pyran derivatives in good to excellent yield with trans selectivity. Application to the synthesis of NK1 antagonist

  手性的反应顺式-和反式-6-（叔-butyldimethylsilyloxy）-3,6-二氢-2 H ^ -吡喃-3-基乙酸酯在存在各种亲核（烯丙基三甲基硅烷，bistrimethylsilylacetylene，苄醇，苄基氨基甲酸叔丁酯等）路易斯酸的生成，以反式选择性好至极好产率得到相应的2，3-不饱和吡喃衍生物。还描述了在NK 1拮抗剂的合成中的应用。
• ¹³C NMR Analysis of 3,6-Dihydro-2<i>H</i>-pyrans: Assignment of Remote Stereochemistry Using Axial Shielding Effects
  作者：Mark J. Bartlett、Peter T. Northcote、Matthias Lein、Joanne E. Harvey

  DOI：10.1021/jo500678k

  日期：2014.6.20

  The rational analysis of 13C NMR axial shielding effects has enabled the assignment of remote relative stereochemistry in 3,6-oxygen-substituted 3,6-dihydro-2H-pyrans. Comparison of the 13C NMR shifts of equivalent centers in cis- and trans-substituted 3,6-dihydro-2H-pyrans allows the relative configuration at the C3 and C6 positions to be defined in diastereoisomeric mixtures. Density functional calculations

  对13 C NMR轴向屏蔽效应的合理分析已使3,6-氧-取代的3,6-二氢-2 H-吡喃具有较远的相对立体化学。比较顺式和反式取代的3,6-二氢-2 H-吡喃中等价中心的13 C NMR位移，可以在非对映异构体混合物中定义C3和C6位置的相对构型。密度泛函计算用于验证该方法并评估环系统中存在的构象偏差。最终，计算化学与这13种方法的耦合基于13 C NMR的方法为单一非对映异构体的立体化学分配提供了可靠且方便的方法。该方法为先前用于确定3，6-二氢-2 H-吡喃的相对构型的方法提供了一种简便且互补的替代方法。
• Design, Synthesis, and Phenotypic Profiling of Pyrano‐Furo‐Pyridone Pseudo Natural Products
  作者：Andreas Christoforow、Julian Wilke、Aylin Binici、Axel Pahl、Claude Ostermann、Sonja Sievers、Herbert Waldmann

  DOI：10.1002/anie.201907853

  日期：2019.10.7

  Natural products (NPs) inspire the design and synthesis of novel biologically relevant chemical matter, for instance through biology-oriented synthesis (BIOS). However, BIOS is limited by the partial coverage of NP-like chemical space by the guiding NPs. The design and synthesis of "pseudo NPs" overcomes these limitations by combining NP-inspired strategies with fragment-based compound design through

  天然产物 (NP) 激发了新型生物学相关化学物质的设计和合成，例如通过面向生物学的合成 (BIOS)。然而，BIOS 受到引导 NP 对类 NP 化学空间的部分覆盖的限制。“伪纳米粒子”的设计和合成克服了这些限制，通过将纳米粒子衍生的片段与生物合成无法获得的前所未有的化合物类别相结合，将纳米粒子启发的策略与基于片段的化合物设计相结合。我们描述了吡喃并呋喃吡啶酮（PFP）假纳米颗粒的开发和生物学评价，该纳米颗粒将吡啶酮和二氢吡喃纳米颗粒片段以三种异构体排列组合在一起。化学信息学分析表明，PFP 位于类似 NP 的化学空间区域，该区域未被现有 NP 覆盖，而是被药物和相关化合物覆盖。与目标无关的“细胞绘画”测定中的表型分析表明，PFP 诱导活性氧的形成，并且是结构新颖的线粒体复合物 I 抑制剂。
• Efficient and practical synthesis of both enantiomers of 6-silyloxy-3-pyranone derivatives
  作者：Kazutoshi Sugawara、Yasuhiro Imanishi、Tomiki Hashiyama

  DOI：10.1016/s0957-4166(00)00424-9

  日期：2000.11

  Lipase catalyzed kinetic resolution of racemic cis-6-(tert-butyldimethylsilyloxy)-3,6-dihydro-2H-pyran-3-ol (rac)-1 was achieved in high enantiomeric excess. Transesterification of (rac)-1 with vinylacetate in 'BuOMe yielded the alcohol (3S,6R)-1 in 99.0% ee, whereas (3R,6S)-1 was obtained, in 99.0% ee, by the lipase catalyzed ester hydrolysis of acetate (3R,6S)-2, which was obtained along with the transesterification. Both (3S,6R)-1 and (3R,6S)-1 were subjected to oxidation to provide the corresponding 6-silyloxy-3-pyranone (6R)-3 and (6S)-3, respectively. Application to the synthesis of 7, which is the key intermediate of asymmetric synthesis of pseudomonic acid A 9 is also described. (C) 2000 Elsevier Science Ltd. All rights reserved.