(E)-3-(4-Benzyloxy-phenyl)-acrylic acid (2S,3R,4S,5R,6R)-4,5-bis-benzyloxy-6-benzyloxymethyl-2-((2aS,4S,4aR,5S,7bS)-4-methyl-1-oxo-2a,3,4,4a,5,7b-hexahydro-1H-2,6-dioxa-cyclopenta[cd]inden-5-yloxy)-tetrahydro-pyran-3-yl ester | 850835-77-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-3-(4-Benzyloxy-phenyl)-acrylic acid (2S,3R,4S,5R,6R)-4,5-bis-benzyloxy-6-benzyloxymethyl-2-((2aS,4S,4aR,5S,7bS)-4-methyl-1-oxo-2a,3,4,4a,5,7b-hexahydro-1H-2,6-dioxa-cyclopenta[cd]inden-5-yloxy)-tetrahydro-pyran-3-yl ester
• 英文别名: [(2S,3R,4S,5R,6R)-2-[[(4S,6S,7R,8S,11S)-6-methyl-2-oxo-3,9-dioxatricyclo[5.3.1.04,11]undec-1(10)-en-8-yl]oxy]-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] (E)-3-(4-phenylmethoxyphenyl)prop-2-enoate
• CAS: 850835-77-7
• 化学式: C₅₃H₅₂O₁₁
• 分子量: 864.989
• InChiKey: LFTMNIDMPSZCPL-UVPULHPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  64
• 可旋转键数：
  19
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  (E)-3-(4-Benzyloxy-phenyl)-acrylic acid (2S,3R,4S,5R,6R)-4,5-bis-benzyloxy-6-benzyloxymethyl-2-((2aS,4S,4aR,5S,7bS)-4-methyl-1-oxo-2a,3,4,4a,5,7b-hexahydro-1H-2,6-dioxa-cyclopenta[cd]inden-5-yloxy)-tetrahydro-pyran-3-yl ester 在 palladium on activated charcoal 氢气 作用下， 以 苯 、 甲醇 、 乙酸乙酯 为溶剂， 反应 2.5h， 以84%的产率得到(-)-littoralisone
  参考文献：
  名称：

  Total Synthesis of Brasoside and Littoralisone

  摘要：

  The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed alpha-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2.

  DOI：

  10.1021/ja050064f
• 作为产物：
  描述：

  (E,3R,5S)-7-(methoxycarbonyl)-5-hydroxy-3-methylhept-6-enyl 2,4,6-trimethylbenzoate 在 咪唑 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 三氟甲磺酸三甲基硅酯 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 氟化氢吡啶 、 N,N'-二环己基碳二亚胺 、 L-脯氨酸 、 三氯氧磷 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 乙腈 、 叔丁醇 为溶剂， 反应 256.67h， 生成 (E)-3-(4-Benzyloxy-phenyl)-acrylic acid (2S,3R,4S,5R,6R)-4,5-bis-benzyloxy-6-benzyloxymethyl-2-((2aS,4S,4aR,5S,7bS)-4-methyl-1-oxo-2a,3,4,4a,5,7b-hexahydro-1H-2,6-dioxa-cyclopenta[cd]inden-5-yloxy)-tetrahydro-pyran-3-yl ester
  参考文献：
  名称：

  Total Synthesis of Brasoside and Littoralisone

  摘要：

  The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed alpha-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2.

  DOI：

  10.1021/ja050064f

文献信息

• Total Synthesis of Brasoside and Littoralisone
  作者：Ian K. Mangion、David W. C. MacMillan

  DOI：10.1021/ja050064f

  日期：2005.3.1

  The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed alpha-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2.