Guo Jianyun, Balić Pascal, Borodkin Vladimir S, Filippov Dmitri V, Codée Jeroen D C
Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, Netherlands.
Division of Molecular Cell and Developmental Biology, School of Life Sciences, University of Dundee, Dow Street, DD1 5EH Dundee, U.K.
Org Lett. 2024 Jan 26;26(3):739-744. doi: 10.1021/acs.orglett.3c04211. Epub 2024 Jan 12.
We demonstrate the use of the symmetrical diethyl(dimethyl)difluoromethylene bisphosphonate reagent for the synthesis of terminal and unsymmetrical difluoromethylene bisphosphonates, close analogues of biologically important molecules. The difference in reactivity of the methyl and ethyl groups in the symmetrical diethyl(dimthyl)difluoromethylene bisphosphonate is exploited in a stepwise demethylation-condensation sequence to functionalize either side of the reagent to allow the generation of a series of close bioisosteres of natural pyrophosphate molecules, including ADPr, CDP-glycerol and CDP-ribitol.
我们展示了对称二乙基（二甲基）二氟亚甲基双膦酸酯试剂在合成末端和不对称二氟亚甲基双膦酸酯中的应用，这些是具有重要生物学意义分子的紧密类似物。对称二乙基（二甲基）二氟亚甲基双膦酸酯中甲基和乙基反应性的差异被用于逐步脱甲基 - 缩合序列中，以使试剂的任一侧官能化，从而生成一系列天然焦磷酸分子的紧密生物电子等排体，包括二磷酸腺苷核糖、胞苷二磷酸甘油和胞苷二磷酸核糖醇。
