(5R,5aR,8S,8aS,8bS)-1,3-dibenzyl-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-8b-hydroxy-7-(4-methylphenyl)sulfonyl-8-[tri(propan-2-yl)silyloxymethyl]-5,5a,8,8a-tetrahydropyrrolo[3,4-e]benzimidazole-2,6-dione | 345642-46-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: (5R,5aR,8S,8aS,8bS)-1,3-dibenzyl-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-8b-hydroxy-7-(4-methylphenyl)sulfonyl-8-[tri(propan-2-yl)silyloxymethyl]-5,5a,8,8a-tetrahydropyrrolo[3,4-e]benzimidazole-2,6-dione
• CAS: 345642-46-8
• 化学式: C₄₇H₆₇N₃O₇SSi₂
• 分子量: 874.302
• InChiKey: UYOSMPKVFANCMT-CTPJOKSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.68
• 重原子数：
  60
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  125
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (5R,5aR,8S,8aS,8bS)-1,3-dibenzyl-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-8b-hydroxy-7-(4-methylphenyl)sulfonyl-8-[tri(propan-2-yl)silyloxymethyl]-5,5a,8,8a-tetrahydropyrrolo[3,4-e]benzimidazole-2,6-dione 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 生成
  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 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 sodium hexamethyldisilazane 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 108.0h， 生成 (5R,5aR,8S,8aS,8bS)-1,3-dibenzyl-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-8b-hydroxy-7-(4-methylphenyl)sulfonyl-8-[tri(propan-2-yl)silyloxymethyl]-5,5a,8,8a-tetrahydropyrrolo[3,4-e]benzimidazole-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

• Enantioselective Strategy to the Spirocyclic Core of Palau'amine and Related Bisguanidine Marine Alkaloids
  作者：Anja S. Dilley、Daniel Romo

  DOI：10.1021/ol015864j

  日期：2001.5.1

  enantioselective strategy to the spirocyclic core found in the oroidin-derived family of bisguanidine marine alkaloids has been devised, premised on a biosynthetic proposal. Herein, we describe the successful implementation of this strategy, which entails a Diels-Alder reaction and a chlorination/ring contraction sequence that delivers the fully functionalized spirocyclic core. In this initial report, an intermolecular

  [结构：见正文]在生物合成方案的基础上，已设计出一种对映体选择性策略，该策略是在源自鸟苷的双胍海洋生物碱家族中发现的螺环核心。在本文中，我们描述了该策略的成功实施，该策略涉及Diels-Alder反应和提供完全功能化螺环核心的氯化/环收缩序列。在该初始报告中，分子间氯化反应生成的环戊烷在C17处相对于帕劳胺而言是异构体，在C11时相对于乙酰丙胺而言是异构体。
• Planned and unplanned halogenations in route to selected oroidin alkaloids
  作者：Shaohui Wang、Anja S. Dilley、Karine G. Poullennec、Daniel Romo

  DOI：10.1016/j.tet.2006.01.115

  日期：2006.7

  stereochemistry, suggested a modification of the Scheuer/Kinnel proposal that may account for the related natural product massadine. Two unsuccessful routes to access the stereochemistry proposed for palau'amine were SN2 displacement of the bromo- and iodocyclopentane with excess chloride anion and an intramolecular directed chlorination pathway. Finally, an unexpected chlorination during our phakellstatin

  高度非对映选择性，受底物控制的卤化/环收缩序列可提供天然存在的氯化和非天然溴化和碘化的乙酰丙胺核心结构。氯化环戊烷发生意外的叠氮化物置换，并保留了立体化学，这表明对Scheuer / Kinnel提案的修改可能涉及相关的天然产物马萨定。S N无法获得提出的有关帕劳胺的立体化学方法2用过量的氯阴离子和分子内定向氯化途径置换溴代和碘代环戊烷。最终，在我们的phakellstatin合成过程中发生了意外的氯化反应，在甲苯磺酸化过程中保留了立体化学，这可能是由于邻近基团的参与所致。