碳水化合物衍生的手性膦及其配位的cis-和trans-铂(II)化合物的合成
收稿日期: 2014-04-18
修回日期: 2014-04-28
网络出版日期: 2014-05-07
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
Received date: 2014-04-18
Revised date: 2014-04-28
Online 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).
通过硼烷对三级有机膦的配位保护，避开了甲基化试剂对膦官能团的季膦化作用，以甘露糖环氧物为原料经4步反应以55%总产率制得甲基2-O-甲基-3-脱氧-3-二苯膦基-4，6-O-苯次甲基-α-D-吡喃阿糖苷(5). 制得的含碳水化合物单元的新手性膦5分别与cis-[Pt(DMSO)2Cl2]和trans-[Pt(NCMe)2Cl2]反应制得相应的cis-和trans-[Pt(5)2Cl2] (6和7). 实验中发现：(1)在烷氧根负离子存在时，硼烷优先与三级膦配位形成膦硼烷加合物; (2)室温下四氢呋喃中糖环上二级醇形成的烷氧根锂盐不能有效地与碘甲烷发生反应，而相应的钠盐顺利地形成目标产物; (3)有机碱是有效的脱硼烷试剂，而乙醇则有更好的反应结果，后处理简便且可几乎定量地得到产物; (4)偶合常数1JPt-P可作为指认这类含碳水化合物单元的手性膦配位的Pt(II)络合物几何构型的可靠参数.
郑珊 , 贾莉 , 刘志森 , 蒋达洪 , 黄艳仙 , 农兰平 , 张庆 , 施继成 . 碳水化合物衍生的手性膦及其配位的cis-和trans-铂(II)化合物的合成[J]. 有机化学, 2014 , 34(9) : 1840 -1844 . DOI: 10.6023/cjoc201404034
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
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