(5R,5aS,8S,8aS)-3-(3,4-Dimethoxy-benzyl)-5-hydroxymethyl-7-(toluene-4-sulfonyl)-1-[2-(toluene-4-sulfonyl)-ethyl]-8-triisopropylsilanyloxymethyl-1,3,4,5,5a,7,8,8a-octahydro-imidazo[4,5-e]isoindole-2,6-dione | 852615-09-9

• 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: (5R,5aS,8S,8aS)-3-(3,4-Dimethoxy-benzyl)-5-hydroxymethyl-7-(toluene-4-sulfonyl)-1-[2-(toluene-4-sulfonyl)-ethyl]-8-triisopropylsilanyloxymethyl-1,3,4,5,5a,7,8,8a-octahydro-imidazo[4,5-e]isoindole-2,6-dione
• 英文别名: (5R,5aS,8S,8aS)-3-[(3,4-dimethoxyphenyl)methyl]-5-(hydroxymethyl)-7-(4-methylphenyl)sulfonyl-1-[2-(4-methylphenyl)sulfonylethyl]-8-[tri(propan-2-yl)silyloxymethyl]-5,5a,8,8a-tetrahydro-4H-pyrrolo[3,4-e]benzimidazole-2,6-dione
• CAS: 852615-09-9
• 化学式: C₄₅H₆₁N₃O₁₀S₂Si
• 分子量: 896.211
• InChiKey: AUOKNMJCJRDTAN-XBYPNEOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.46
• 重原子数：
  61
• 可旋转键数：
  17
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  177
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (5R,5aS,8S,8aS)-3-(3,4-Dimethoxy-benzyl)-5-hydroxymethyl-7-(toluene-4-sulfonyl)-1-[2-(toluene-4-sulfonyl)-ethyl]-8-triisopropylsilanyloxymethyl-1,3,4,5,5a,7,8,8a-octahydro-imidazo[4,5-e]isoindole-2,6-dione 在 二甲基二环氧乙烷 、 magnesium sulfate 、 三乙胺 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 2.0h， 生成 2,2-dimethyl-propionic acid 3-(3,4-dimethoxy-benzyl)-8b-hydroxy-2,6-dioxo-7-(toluene-4-sulfonyl)-1-[2-(toluene-4-sulfonyl)-ethyl]-8-triisopropylsilanyloxymethyl-1,2,3,5,5a,6,7,8,8a,8b-decahydro-imidazo[4,5-e]isoindol-5-ylmethyl ester
  参考文献：
  名称：

  A unified synthetic strategy toward oroidin-derived alkaloids premised on a biosynthetic proposal

  摘要：

  Details of the evolution of a synthetic strategy toward the spirocyclic chlorocyclopentane core of oroidin-derived alkaloids, including the axinellamines and potentially adaptable to palau'amine, are described. A proposed refinement of the Kinnel-Scheuer biosynthetic proposal for palau'amine is posited. Studies undertaken to improve the regioselectivity and efficiency of a key Diels-Alder reaction utilizing a novel protecting group strategy, microwave chemistry, and other strategies are described. Further insights regarding the suitability of different protecting groups during the epoxidation/chlorination/ring contraction sequence are disclosed. Several interesting by-products from this reaction sequence are reported. These studies have led to a unified synthetic strategy to the axinellamines and palau'amine. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.12.068
• 作为产物：
  描述：

  L-焦谷氨酸甲酯 在 咪唑 、 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 sodium hexamethyldisilazane 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醇 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 1.0h， 生成 (5R,5aS,8S,8aS)-3-(3,4-Dimethoxy-benzyl)-5-hydroxymethyl-7-(toluene-4-sulfonyl)-1-[2-(toluene-4-sulfonyl)-ethyl]-8-triisopropylsilanyloxymethyl-1,3,4,5,5a,7,8,8a-octahydro-imidazo[4,5-e]isoindole-2,6-dione
  参考文献：
  名称：

  A unified synthetic strategy toward oroidin-derived alkaloids premised on a biosynthetic proposal

  摘要：

  Details of the evolution of a synthetic strategy toward the spirocyclic chlorocyclopentane core of oroidin-derived alkaloids, including the axinellamines and potentially adaptable to palau'amine, are described. A proposed refinement of the Kinnel-Scheuer biosynthetic proposal for palau'amine is posited. Studies undertaken to improve the regioselectivity and efficiency of a key Diels-Alder reaction utilizing a novel protecting group strategy, microwave chemistry, and other strategies are described. Further insights regarding the suitability of different protecting groups during the epoxidation/chlorination/ring contraction sequence are disclosed. Several interesting by-products from this reaction sequence are reported. These studies have led to a unified synthetic strategy to the axinellamines and palau'amine. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.12.068

文献信息

• Highly Regioselective Diels−Alder Reactions toward Oroidin Alkaloids:  Use of a Tosylvinyl Moiety as a Nitrogen Masking Group with Adjustable Electronics
  作者：Paul J. Dransfield、Shaohui Wang、Anja Dilley、Daniel Romo

  DOI：10.1021/ol0473602

  日期：2005.4.1

  [reaction: see text] The use of the p-toluenesulfonyl (Ts) and tosylvinyl (Tsv) groups as nitrogen masking groups imparted high regioselectivity in Diels-Alder reactions directed toward members of the oroidin-derived marine alkaloid family. The electron-withdrawing Tsv group was utilized as an electronically adjustable nitrogen-protecting group as subsequent hydrogenation provided the more electron-rich

  [反应：见正文]对甲苯磺酰基（Ts）和甲苯磺酰基（Tsv）基团作为氮掩蔽基团的使用在Diels-Alder反应中赋予了高区位选择性，该反应是针对得自麦冬蛋白的海洋生物碱家族的成员。吸电子的Tsv基团被用作电子可调的氮保护基团，因为随后的氢化提供了更富电子的甲苯磺酰基（Tse）基团。这种电子调节策略避免了保护基团的交换，并为关键的氯化/环缩合顺序提供了所需的电子设备。