Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (12): 3351-3355.DOI: 10.6023/cjoc201806028 Previous Articles     Next Articles


海洋天然核苷Kipukasin D的首次全合成

丁海新a, 李闯a, 董祥有a, 曹伴鹏a, 张宁b, 洪三国b, 肖强a   

  1. a 江西科技师范大学有机功能分子研究所 江西省有机功能分子重点实验室 南昌 330013;
    b 南昌大学化学学院 南昌 330031
  • 收稿日期:2018-06-19 修回日期:2018-07-11 发布日期:2018-08-23
  • 通讯作者: 肖强
  • 基金资助:


First Total Synthesis of Marine Natural Nucleoside Kipukasin D

Ding Haixina, Li Chuanga, Dong Xiangyoua, Cao Banpena, Zhang Ningb, Hong Sanguob, Xiao Qianga   

  1. a Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang 330013;
    b Department of Chemistry, Nanchang University, Nanchang 330031
  • Received:2018-06-19 Revised:2018-07-11 Published:2018-08-23
  • Contact: 10.6023/cjoc201806028
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21462019, 21676131), the Bureau of Science & Technology of Jiangxi Province (No. 20143ACB20012) and the Education Department of Jiangxi Province (No. 170673).

The first total synthesis of marine natural nucleoside kipukasin D was disclosed in 9 steps and 15.7% overall yield using commercially available tetra-O-acetyl-β-D-ribose as starting material. In Vorbrüggen glycosylation, ortho-iodinebenzoate acted as neighboring participating group leading to β-nucleoside. The key step was selectively deprotection of 2'-O and 5'-O ortho-alkynylbenzoates by freshing prepared Ph3PAuOTFA in the presence of ethanol (6 equiv.) and H2O (1 equiv.) in dichloromethane (DCM). The reaction condition of our newly developed approach is very mild and neutral, which effectively avoids the transesterification between 2'-OH and 3'-OH. The result further demonstrat that ortho-alkynylbenzoate is an orthogonal protecting group compatible with other ester groups, which could find wide applications in nucleoside and carbohydrate chemistry.

Key words: nucleoside, neighboring-group, transesterification, catalysis, total synthesis