(3aS,4R,6R,7aS)-6-Allyl-4-(tert-butyl-diphenyl-silanyloxymethyl)-tetrahydro-[1,3]dioxolo[4,5-c]pyran-2-one | 874660-33-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (3aS,4R,6R,7aS)-6-Allyl-4-(tert-butyl-diphenyl-silanyloxymethyl)-tetrahydro-[1,3]dioxolo[4,5-c]pyran-2-one
• 英文别名: (3aS,4R,6R,7aS)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-6-prop-2-enyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one
• CAS: 874660-33-0
• 化学式: C₂₆H₃₂O₅Si
• 分子量: 452.623
• InChiKey: AZCOWRVNXYWDJW-GOUWZUTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  (3aS,4R,6R,7aS)-6-Allyl-4-(tert-butyl-diphenyl-silanyloxymethyl)-tetrahydro-[1,3]dioxolo[4,5-c]pyran-2-one 在 9-borabicyclo[3.3.1]nonane dimer 、 4-甲基苯磺酸吡啶 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 18.5h， 生成 3-[(3aS,4R,6R,7aS)-4-[[tert-butyl(diphenyl)silyl]oxymethyl]-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]propan-1-ol
  参考文献：
  名称：

  Convergent, Stereoselective Synthesis of the GHIJ Fragment of Brevetoxin A

  摘要：

  A stereoselective synthesis of the GHIJ fragment of brevetoxin A utilizing a convergent assembly strategy is described. Glycolate alkylation, ring-closing metathesis, and Hosomi-Sakurai reactions were central operations in the construction of the G ring and J ring subunits, which were united through a Horner-Wadsworth-Emmons coupling. Subsequent dehydrative cyclization produced an endocyclic enol ether that was further elaborated to the tetracyclic GHIJ fragment of brevetoxin A.

  DOI：

  10.1021/ol0526625
• 作为产物：
  描述：

  tert-butyl[(2S)-oxiran-2-ylmethoxy]diphenylsilane 在 ruthenium trichloride 、 sodium periodate 、 Grubbs catalyst first generation 、 正丁基锂 、 pyridium para-toluenesulfonate 、 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 、 苯 为溶剂， 反应 5.52h， 生成 (3aS,4R,6R,7aS)-6-Allyl-4-(tert-butyl-diphenyl-silanyloxymethyl)-tetrahydro-[1,3]dioxolo[4,5-c]pyran-2-one
  参考文献：
  名称：

  Convergent, Stereoselective Synthesis of the GHIJ Fragment of Brevetoxin A

  摘要：

  A stereoselective synthesis of the GHIJ fragment of brevetoxin A utilizing a convergent assembly strategy is described. Glycolate alkylation, ring-closing metathesis, and Hosomi-Sakurai reactions were central operations in the construction of the G ring and J ring subunits, which were united through a Horner-Wadsworth-Emmons coupling. Subsequent dehydrative cyclization produced an endocyclic enol ether that was further elaborated to the tetracyclic GHIJ fragment of brevetoxin A.

  DOI：

  10.1021/ol0526625

文献信息

• Enantioselective Total Synthesis of Brevetoxin A: Unified Strategy for the B, E, G, and J Subunits
  作者：Michael T. Crimmins、J. Michael Ellis、Kyle A. Emmitte、Pamela A. Haile、Patrick J. McDougall、Jonathan D. Parrish、J. Lucas Zuccarello

  DOI：10.1002/chem.200900776

  日期：2009.9.14

  oxacycles, as well as 22 tetrahedral stereocenters. Herein, we describe a unified approach to the B, E, G, and J rings based upon a ring‐closing metathesis strategy from the corresponding dienes. The enolate technologies developed in our laboratory allowed access to the precursor acyclic dienes for the B, E, and G medium‐ring ethers. The strategies developed for the syntheses of these four monocycles

  Brevetoxin A 是一种十环梯形毒素，具有 5、6、7、8 和 9 元氧杂环，以及 22 个四面体立体中心。在此，我们描述了基于来自相应二烯的闭环复分解策略的 B、E、G 和 J 环的统一方法。我们实验室开发的烯醇技术允许获得 B、E 和 G 中环醚的前体无环二烯。为合成这四个单环而开发的策略最终提供了数克数量的每个环，支持我们为完成短毒素 A 的收敛合成所做的努力。
• Convergent, Stereoselective Synthesis of the GHIJ Fragment of Brevetoxin A
  作者：Michael T. Crimmins、J. Lucas Zuccarello、Pamela A. Cleary、Jonathan D. Parrish

  DOI：10.1021/ol0526625

  日期：2006.1.1

  A stereoselective synthesis of the GHIJ fragment of brevetoxin A utilizing a convergent assembly strategy is described. Glycolate alkylation, ring-closing metathesis, and Hosomi-Sakurai reactions were central operations in the construction of the G ring and J ring subunits, which were united through a Horner-Wadsworth-Emmons coupling. Subsequent dehydrative cyclization produced an endocyclic enol ether that was further elaborated to the tetracyclic GHIJ fragment of brevetoxin A.