Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (1): 238-248.DOI: 10.6023/cjoc201805023 Previous Articles     Next Articles

Special Issue: 庆祝陈庆云院士九十华诞



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 发布日期:2018-09-26
  • 通讯作者: 龚建贤, 杨震;
  • 基金资助:


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 Published:2018-09-26
  • Contact: 10.6023/cjoc201805023;
  • 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).

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