Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (9): 1840-1844.DOI: 10.6023/cjoc201404034 Previous Articles     Next Articles


郑珊a,b, 贾莉b, 刘志森a, 蒋达洪a, 黄艳仙a, 农兰平a, 张庆a, 施继成a,b   

  1. a 广东石油化工学院, 化学工程学院, 茂名 525000;
    b 福建师范大学, 福建省高分子材料重点实验室, 福州 350007
  • 收稿日期:2014-04-18 修回日期:2014-04-28 发布日期:2014-05-07
  • 通讯作者: 贾莉, 施继成;
  • 基金资助:

    国家自然科学基金(No. 212723037)和福建省自然科学基金(No. 2011J01033)资助项目.

Synthesis of a New Carbohydrate-Derived Chiral Phosphine and Its Coordinating cis- and trans-Pt(II) Complexes

Zheng Shana,b, Jia Lib, Liu Zhisena, Jiang Dahonga, Huang Yanxiana, Nong Nanpinga, Zhang Qinga, Shi Jichenga,b   

  1. a College of Chemical Engineering, Guangdong University of Petrochemical Technology, Maoming 525000;
    b Key Laboratory of Polymer Materials of Fujian Province, Fujian Normal University, Fuzhou 350007
  • Received:2014-04-18 Revised:2014-04-28 Published:2014-05-07
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21272037) and the Natural Science Foundation of Fujian Province (No. 2011J01033).

Via four steps of nucleophilic ring-opening of α-D-manno-epoxide with Ph2P- anion, adduction of boranes to phospnine, methylation of hydroxyl, and deprotection of the phosphine-boranes adduct, afforded the desired methyl 3-deoxy-3-diphenylphosphino-2-O-methyl-4,6-O-phenylmethenyl-α-D-pyranoaltroside (5) in 55% of yield. It was found that: (1) the adduct of boranes to the carbohydrate-based phosphine was formed smoothly in the presence of alkyloxide, (2) the alkoxide derived from the secondary alcohol of pyranoside was methylized with MeI as in its sodium salt other than in lithium salt in THF at room temperature, and (3) the deprotection of boranes from the carbohydrate-based phosphine adduct went smoothly by several of organic bases, but more efficiently by ethanol. The corresponding cis- and trans-[Pt(5)2Cl2] formed by the reaction of the carbohydrate-based phosphine 5 with cis- and trans-[Pt(NCMe)2Cl2], respectively. The coupling constant 1JPt-P was reliable to assign the configuration of the geometrical stereoisomers of Pt(II) complexes with the carbohydrate-based phosphine.

Key words: carbohydrate, chiral phosphine, deboronation, Pt(II) complex