(8R,8aS)-8-benzyloxy-3,5,6,7,8,8a-hexahydroindolizine | 476171-52-5

• 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: (8R,8aS)-8-benzyloxy-3,5,6,7,8,8a-hexahydroindolizine
• 英文别名: (8R,8aS)-8-phenylmethoxy-1,2-dehydroindolizine；(8R,8aS)-8-phenylmethoxy-3,5,6,7,8,8a-hexahydroindolizine
• CAS: 476171-52-5
• 化学式: C₁₅H₁₉NO
• 分子量: 229.322
• InChiKey: YDWDSGKMMVZVGA-LSDHHAIUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (8R,8aS)-8-benzyloxy-3,5,6,7,8,8a-hexahydroindolizine 在 甲基磺酰胺 、 potassium carbonate 盐酸 、 potassium osmate(VI) 、 Hydroquinone 1,4-phthalazinediyl diether 、 氢气 、 对甲苯磺酸 、 palladium dichloride 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 193.5h， 生成 八倾吲嗪三醇
  参考文献：
  名称：

  Asymmetric Synthesis of (−)-Swainsonine, (+)-1,2-Di-epi-swainsonine, and (+)-1,2,8-Tri-epi-swainsonine

  摘要：

  The asymmetric synthesis of H-swainsonine via a nonchiral pool route that involves the Sharpless epoxidation to induce chirality is reported. The key steps involve vinyl epoxide aminolysis, ring-closing metathesis, and intramolecular N-alkylation to prepare the indolizidine ring and a highly diastereoselective cis-dihydroxylation using AD-mix-cc. This synthetic strategy also allowed for the diastereoselective synthesis of (+)-1,2-di-epi-swainsonine and (+)-1,2,8-tri-epi-swainsonine.

  DOI：

  10.1021/jo025977w
• 作为产物：
  描述：

  7-[(4-甲氧基苯基)甲氧基]-(3R,4R)-环氧-1-庚烯 在 Grubbs catalyst first generation 、 四溴化碳 、 四丁基碘化铵 、 sodium hydride 、 对甲苯磺酸 、 苯甲醚 、 三乙胺 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 285.67h， 生成 (8R,8aS)-8-benzyloxy-3,5,6,7,8,8a-hexahydroindolizine
  参考文献：
  名称：

  Asymmetric Synthesis of (−)-Swainsonine, (+)-1,2-Di-epi-swainsonine, and (+)-1,2,8-Tri-epi-swainsonine

  摘要：

  The asymmetric synthesis of H-swainsonine via a nonchiral pool route that involves the Sharpless epoxidation to induce chirality is reported. The key steps involve vinyl epoxide aminolysis, ring-closing metathesis, and intramolecular N-alkylation to prepare the indolizidine ring and a highly diastereoselective cis-dihydroxylation using AD-mix-cc. This synthetic strategy also allowed for the diastereoselective synthesis of (+)-1,2-di-epi-swainsonine and (+)-1,2,8-tri-epi-swainsonine.

  DOI：

  10.1021/jo025977w

文献信息

• Palladium-Catalysed Cyclisation of α-Hydroxy Allylic Acetates: A Formal Synthesis of (±)-Swainsonine
  作者：Roderick Bates、Mark Dewey、Chi Tang、Shahidah Safii、Yanhan Hong、Jolyn Hsieh、Pei Siah

  DOI：10.1055/s-0030-1260952

  日期：2011.9

  A hydroxy group in the allylic position directed the stereochemistry of cyclisation of allylic acetates to form nitrogen heterocycles, giving the trans isomer for the piperidine and the cis isomer for the pyrrolidine. A formal synthesis of (±)-swainsonine was achieved. piperidine - palladium - pyrrolidine - alkaloid - cyclisation

  烯丙基位置的羟基指导乙酸烯丙基乙酸酯环化形成氮杂环的立体化学，从而形成哌啶的反式异构体和吡咯烷的顺式异构体。正式合成了（±）-swainsonine。 哌啶-钯-吡咯烷-生物碱-环化
• A concise formal stereoselective total synthesis of (−)-swainsonine
  作者：Xiao-Gang Wang、Ai-E Wang、Pei-Qiang Huang

  DOI：10.1016/j.cclet.2013.12.003

  日期：2014.2

  A short formal stereoselective synthesis of (−)-swainsonine (1) is described. Our synthesis started with the versatile building block (R)-3-benzyloxyglutarimide 5. Through controlled regioselective reduction, Ley's-sulfone chemistry (N-α-sulfonylation and ZnCl2-catalyzed N-α-amidovinylation), an RCM reaction, and an amide reduction, the synthesis of unsaturated indolizidine (8R,8aS)-3 has been achieved

  描述了（-）-swainsonine（1）的简短形式立体选择性合成。我们的合成始于通用的结构单元（R）-3-苄氧基戊二酰亚胺5。通过控制区域选择性还原，莱氏砜化学反应（N - α-磺酰化和ZnCl 2催化的N - α-酰胺基乙烯基化），RCM反应和酰胺还原反应，可以合成不饱和吲哚并咪唑（8 R，8a S）-3已通过五个步骤实现。吲哚并咪唑（8 R，8a S）-3是合成（-）-swainsonine（1）的高级中间体。
• Asymmetric Formal Synthesis of (–)-Swainsonine from Chiral-Pool Precursors d-Mannose and d-Arabinose
  作者：Anphisa Lamor、Suwanan Uipanit、Nutthawat Chuanopparat、Sujitra Yakhampom、Paiboon Ngernmeesri、Ngampong Kongkathip、Boonsong Kongkathip

  DOI：10.1055/s-0041-1737335

  日期：2022.9

  played an important role in organic synthesis. Since they contain many stereocenters, they have been widely used as chiral-pool starting materials. Herein, we report the asymmetric formal synthesis of (–)-swainsonine, which exhibits anticancer and immunosuppressive activities and inhibits lysosomal α-mannosidase activity, from d-mannose and d-arabinose. The synthesis utilized Zn-mediated Bernet–Vasella

  碳水化合物在有机合成中发挥了重要作用。由于它们含有许多立体中心，因此它们已被广泛用作手性池起始材料。在此，我们报告了 (–)-swainsonine 的不对称形式合成，该合成具有抗癌和免疫抑制活性并抑制溶酶体 α-甘露糖苷酶活性，来自d-甘露糖和d-阿拉伯糖。该合成利用 Zn 介导的 Bernet-Vasella 反应、Horner-Wadsworth-Emmons 烯化和 Grubbs 烯烃复分解作为关键反应。
• Asymmetric Synthesis of (−)-Swainsonine, (+)-1,2-Di-<i>epi</i>-swainsonine, and (+)-1,2,8-Tri-<i>epi</i>-swainsonine
  作者：Karl B. Lindsay、Stephen G. Pyne

  DOI：10.1021/jo025977w

  日期：2002.11.1

  The asymmetric synthesis of H-swainsonine via a nonchiral pool route that involves the Sharpless epoxidation to induce chirality is reported. The key steps involve vinyl epoxide aminolysis, ring-closing metathesis, and intramolecular N-alkylation to prepare the indolizidine ring and a highly diastereoselective cis-dihydroxylation using AD-mix-cc. This synthetic strategy also allowed for the diastereoselective synthesis of (+)-1,2-di-epi-swainsonine and (+)-1,2,8-tri-epi-swainsonine.