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2025 , Vol. 45 >Issue 3: 977 - 987

DOI: https://doi.org/10.6023/cjoc202409012

研究论文

Kuroshine类生物碱的合成研究

  • 文国恩 ,
  • 谷硕 ,
  • 何海兵 ,
  • 高栓虎
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  • a 华东师范大学化学与分子工程学院 石油化工分子转化与过程全国重点实验室 上海市绿色化学与化工过程绿色化重点实验室 上海 200062
    b 上海市分子智造前沿科学基地 上海 200062

收稿日期: 2024-09-11

  修回日期: 2024-10-16

  网络出版日期: 2024-12-06

基金资助

国家高新技术研究发展计划(2022YFC2804201); 国家自然科学基金(22225105); 上海市科学技术委员会(22JC1401101)

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Synthetic Study of Kuroshine Alkaloids

  • Guoen Wen ,
  • Shuo Gu ,
  • Haibing He ,
  • Shuanhu Gao
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  • a Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062
    b Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, Shanghai 200062
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Received date: 2024-09-11

  Revised date: 2024-10-16

  Online published: 2024-12-06

Supported by

National High Technology Research and Development Program of China(2022YFC2804201); National Natural Science Foundation of China(22225105); Shanghai Science and Technology Committee(22JC1401101)

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摘要

Kuroshine类生物碱是从Zoanthus中分离得到的高氧化态海洋类天然产物, 其结构复杂多样, 拥有三个全碳季碳中心(C-9、C-12和C-22), 具有密集官能团和高氧化态骨架. 其合成难点主要包括全氢菲的A-B-C三环的构建、邻二季碳中心(C-9、C-22)的构筑及C-11、C-28和C-25位氧化态的精准引入. 对kuroshine类生物碱进行了合成研究, 通过氯甲基锂对烯酮的加成及环氧重排顺利地引入了C-25位的氧化态, 利用分子内的烷基化取代反应成功地构筑了邻二季碳中心(C-9、C-22), 采用二碘化钐介导的单电子开环氧引入了C-12位的氧化态, 完成了其二环醛基片段和手性碘代片段的合成.

关键词： 高氧化态; 烷基化; kuroshine生物碱; 海洋天然产物

本文引用格式

文国恩 , 谷硕 , 何海兵 , 高栓虎 . Kuroshine类生物碱的合成研究[J]. 有机化学, 2025 , 45(3) : 977 -987 . DOI: 10.6023/cjoc202409012

Abstract

Kuroshine alkaloids are highly oxidized marine natural products isolated from Zoanthus, which have complex and diverse structure, including three all carbon quaternary carbon centers (C-9, C-12, and C-22), densely functional groups, and a highly oxidized skeleton. The main syntheic challenges include the construction of the fully hydrogenated phenanthrene A-B-C ring, the construction of adjacent quaternary carbon centers (C-9, C-22), and the precise introduction of oxidation states at C-11, C-28, and C-25 positions. A synthetic study on kuroshine alkaloids was conducted, successfully introducing the C-25 oxidation state through the addition of chloromethyl lithium to enone and epoxide rearrangement, and constructing adjacent quaternary carbon centers (C-9, C-22) through intramolecular alkylation substitution reactions. The C-12 oxidation state was introduced through a single electron epoxide opening mediated by samarium iodide. The synthesis of bicyclic aldehyde fragment 19 and chiral iodo fragment 20 was finally completed.

Key words： high oxidation state; alkylation; kuroshine alkaloid; marine natural product

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