ethyl [2-benzyloxy-6-(tert-butyldimethylsilyloxymethyl)-3,6-dihydro-2H-pyran-3-yl]acetate | 500222-26-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl [2-benzyloxy-6-(tert-butyldimethylsilyloxymethyl)-3,6-dihydro-2H-pyran-3-yl]acetate
• 英文别名: ethyl 2-[(2S,3R,6S)-2-benzyloxy-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-3,6-dihydro-2H-pyran-3-yl]acetate；ethyl 2-[(2S,3R,6S)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2-phenylmethoxy-3,6-dihydro-2H-pyran-3-yl]acetate
• CAS: 500222-26-4
• 化学式: C₂₃H₃₆O₅Si
• 分子量: 420.621
• InChiKey: UDBUFSMBRMICIU-ONTIZHBOSA-N

物化性质

• 沸点：
  456.2±45.0 °C(predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.08
• 重原子数：
  29
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl [2-benzyloxy-6-(tert-butyldimethylsilyloxymethyl)-3,6-dihydro-2H-pyran-3-yl]acetate 在 lithium aluminium tetrahydride 、 pyridinium chlorochromate 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 2-[2-benzyloxy-6-(tert-butyldimethylsilyloxymethyl)-3,6-dihydro-2H-pyran-3-ylmethyl]-2,3-dihydropyran-4-one
  参考文献：
  名称：

  HIGHLY DEOXYGENATED SUGARS. I. C2-BRANCHED GLUCOSE DERIVATIVES AND CARBON LINKED DEOXYGENATED DISACCHARIDES^*

  摘要：

  Triacetylglucal (1) is converted with high alpha-selectivity (>9:1) to the corresponding 2,3-unsaturated allyl and benzyl glycosides 2 and 3 using ferric chloride as the catalyst. The 6-O-silyl-protected allylic alcohol 5 is transformed to the 3,4-unsaturated C2-branched ester 6 or the amide 7 by Claisen rearrangement. The highly deoxygenated iodo lactone 8, resulting from the amide 6 by iodolactonization, is a versatile starting material for chiral building blocks 9-12. The 3,4-unsaturated C2-branched ester 6 is reduced to the aldehyde 14 and converted to a carbon linked disaccharide analogue 16 via cycloaddition with Danishefky's diene.

  DOI：

  10.1081/car-120014904
• 作为产物：
  描述：

  benzyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enpyranoside 在 咪唑 、 4-二甲氨基吡啶 、 potassium carbonate 、 丙酸 作用下， 以 甲醇 、 5,5-dimethyl-1,3-cyclohexadiene 、 二氯甲烷 为溶剂， 反应 36.0h， 生成 ethyl [2-benzyloxy-6-(tert-butyldimethylsilyloxymethyl)-3,6-dihydro-2H-pyran-3-yl]acetate
  参考文献：
  名称：

  通过质子耦合电子转移实现未活化烯烃的催化加氢醚化。

  摘要：

  我们报告了一种催化光驱动方法，用于未活化烯醇的分子内加氢醚化以提供环醚产品。这些反应在 Ir III基光氧化还原催化剂、布朗斯台德碱催化剂和氢原子转移 (HAT) 助催化剂存在下在可见光照射下发生。反应性烷氧基被认为是关键中间体，是通过质子耦合电子转移机制直接均裂激活醇 O−H 键而产生的。该方法表现出广泛的底物范围和高官能团耐受性，并且适应多种烯烃取代模式。还提出了证明该催化系统扩展到碳醚化反应的结果。

  DOI：

  10.1002/anie.202003959

文献信息

• Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton‐Coupled Electron Transfer
  作者：Elaine Tsui、Anthony J. Metrano、Yuto Tsuchiya、Robert R. Knowles

  DOI：10.1002/anie.202003959

  日期：2020.7.13

  We report a catalytic, light‐driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible‐light irradiation in the presence of an IrIII‐based photoredox catalyst, a Brønsted base catalyst, and a hydrogen‐atom transfer (HAT) co‐catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct

  我们报告了一种催化光驱动方法，用于未活化烯醇的分子内加氢醚化以提供环醚产品。这些反应在 Ir III基光氧化还原催化剂、布朗斯台德碱催化剂和氢原子转移 (HAT) 助催化剂存在下在可见光照射下发生。反应性烷氧基被认为是关键中间体，是通过质子耦合电子转移机制直接均裂激活醇 O−H 键而产生的。该方法表现出广泛的底物范围和高官能团耐受性，并且适应多种烯烃取代模式。还提出了证明该催化系统扩展到碳醚化反应的结果。
• HIGHLY DEOXYGENATED SUGARS. I. C2-BRANCHED GLUCOSE DERIVATIVES AND CARBON LINKED DEOXYGENATED DISACCHARIDES^*
  作者：Karsten Krohn、Ulrich Flörke、Dietmar Gehle

  DOI：10.1081/car-120014904

  日期：2002.1.10

  Triacetylglucal (1) is converted with high alpha-selectivity (>9:1) to the corresponding 2,3-unsaturated allyl and benzyl glycosides 2 and 3 using ferric chloride as the catalyst. The 6-O-silyl-protected allylic alcohol 5 is transformed to the 3,4-unsaturated C2-branched ester 6 or the amide 7 by Claisen rearrangement. The highly deoxygenated iodo lactone 8, resulting from the amide 6 by iodolactonization, is a versatile starting material for chiral building blocks 9-12. The 3,4-unsaturated C2-branched ester 6 is reduced to the aldehyde 14 and converted to a carbon linked disaccharide analogue 16 via cycloaddition with Danishefky's diene.