Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (19): 2024-2028.DOI: 10.6023/A12060337 Previous Articles     Next Articles



李玉叶a,b, 黄重行a, 许鹏飞b, 张艳a, 王剑波a   

  1. a 北京大学化学与分子工程学院 生物有机与分子工程教育部重点实验室 北京分子科学国家实验室 北京 100871;
    b 兰州大学 功能有机分子化学国家重点实验室 兰州 730000
  • 投稿日期:2012-06-24 发布日期:2012-09-03
  • 通讯作者: 王剑波
  • 基金资助:

    项目受国家自然科学基金(Nos. 21072009, 21172005);国家重点基础研究发展计划(973 Program, No. 2009CB825300)和教育部留学回国人员科研启动基金资助.

Studies on the Reactivity of Migrating Group in [2,3]-Sigmatropic Rearrangement of Sulfur Ylides

Li Yuyea,b, Huang Zhongxinga, Xu Peng-Feib, Zhang Yana, Wang Jianboa   

  1. a Beijing National Laboratory of Molecular Sciences BNLMS and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China;
    b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China
  • Received:2012-06-24 Published:2012-09-03
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21072009, 21172005), National Basic Research Program of China (973 Program, No. 2009CB825300), The Project Sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.

The [2,3]-sigmatropic rearrangement of sulfur ylides is unique and useful reaction in organic synthesis. In this study, the reactivity of sulfides containing three different migrating groups (propargyl, allyl, and allenyl) in [2,3]-sigmatropic rearrangement of sulfur ylides has been compared. The competition reactions of phenylethyldiazoacetate with sulfides through sulfonium ylide [2,3]-sigmatropic rearrangement are designed under Rh(II)- or Cu(I)-catalyzed reaction conditions. Both intra- and intermolecular competitions of sulfides bearing two different migrating groups have been carried out. The ratio of products has been determined by 1H NMR in order to compare the reactivity of different sulfides bearing allyl, propargyl or allenyl groups. Obvious disparity of the reactivity of these sulfides in [2,3]-sigmatropic rearrangement has been observed. Experimental data indicate that the tendency of preferential [2,3]-sigmatropic rearrangement has the following order: propargyl sulfide>allyl sulfide>allenyl sulfide. Catalysts such as Rh2(OAc)4, Rh2(O2CCF3)4, and Cu(CH3CN)4PF6 ligated with a series of diimine ligands have been investigated for these reactions. Rh(II) complexes are found more efficient than Cu(I) complexes, and Rh2(O2CCF3)4 is more efficient than Rh2(OAc)4. The efficiency of different catalytic system has been explained based on the proposed reaction mechanism. The reaction catalyzed by Rh(II) complexes is suggested to be different from that catalyzed by Cu(I) complexes. In the case of Cu(I)-catalyzed reaction, Cu(I)-bonded sulfur ylide is considered as the predominant intermediate, while the [2,3]-sigmatropic rearrangement is suggested to proceed through free ylide. Both steric hindrance and electronic properties of ligands influence the ratio and selectivity in Cu(I)-catalyzed reactions. This study provides useful information for further investigation of [2,3]-sigmatropic rearrangement of sulfur ylides.

Key words: sulfur ylide, [2,3]-sigmatropic rearrangement, metal carbene, migratory group, catalytic reaction