有机化学 ›› 2019, Vol. 39 ›› Issue (1): 238-248.DOI: 10.6023/cjoc201805023 上一篇    下一篇

所属专题: 庆祝陈庆云院士九十华诞

研究论文

基于分子内交叉氧化偶联反应来非对映选择性构建全碳季碳中心

陈伟a, 郭人予a, 龚建贤a, 杨震a,b   

  1. a 北京大学深圳研究生院 省部共建肿瘤化学基因组学国家重点实验室 深圳 518055;
    b 北京大学 北京分子科学国家重点实验室 生物有机分子工程教育部重点实验室 北京 100871
  • 收稿日期:2018-05-10 修回日期:2018-09-13 出版日期:2019-01-25 发布日期:2018-09-26
  • 通讯作者: 龚建贤, 杨震 E-mail:zyang@pku.edu.cn;gongjx@pku.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21772008,21632002)、深圳市科技计划(No.GRCK2017042414425972)、广东省自然科学基金(No.2016A030306011)和青岛海洋科学与技术国家实验室开放基金(No.LMDBKF201703)资助项目.

Diastereoselective Construction of All-Carbon Quaternary Stereocenters via Intramolecular Oxidative Cross-Coupling Reaction

Chen Weia, Guo Renyua, Gong Jianxiana, Yang Zhena,b   

  1. a State Key Laboratory of Chemical Oncogenomics, Peking University Shenzhen Graduate School, Shenzhen 518055;
    b Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science(BNLMS), Peking University, Beijing 100871
  • Received:2018-05-10 Revised:2018-09-13 Online:2019-01-25 Published:2018-09-26
  • Contact: 10.6023/cjoc201805023 E-mail:zyang@pku.edu.cn;gongjx@pku.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21772008, 21632002), the Shenzhen Science and Technology Project Program (No. GRCK2017042414425972), the Natural Science Foundation of Guangdong Province (No. 2016A030306011) and the Qingdao National Laboratory for Marine Science and Technology (No. LMDBKF201703).

立体位阻拥挤C—C键,尤其是包含全碳季碳中心C—C键的构建一直是现代有机合成化学的挑战.利用硝酸铈铵(CAN)诱导的双烯醇硅醚化合物分子内交叉氧化偶联反应来非对映选择性地构建连续全碳季碳中心以及叔碳中心.该方法在相对温和的反应条件下,以CAN作为单电子氧化剂,高产率、高非对映选择性地构建立体位阻拥挤的C—C键.本研究提供了一种通过分子内交叉氧化偶联反应来实现两个不同片段高效连接的有效手段,可以应用到复杂天然产物的全合成研究中去.

关键词: 氧化偶联反应, 季碳中心, 叔碳中心, 方法学

The formation of sterically hindered C—C bond represents a great challenge in modern synthetic organic chemistry. A particularly challenging issue is the construction of all-carbon quaternary stereocenters. Herein, a ceric ammonium nitrate (CAN)-mediated intramolecular oxidative cross-coupling of silyl ethers for direct construction of valuable polycyclic scaffolds is described. The reaction enables sterically congested vicinal all-carbon quaternary and tertiary stereocenters to be installed diastereoselectively. The developed method provides a concise and efficient approach for ligation of two different segments through a compact C—C bond formation, which has potential applications in the synthesis of complex molecules as well as sterically congested natural products.

Key words: oxidative coupling reaction, quaternary stereocenter, tertiary stereocenter, methodology