engleski

1, 1'-Bis(thymine)ferrocene Nucleoside : Synthesis and Study of Its Stereoselective Formation

The synthesis of 1, 1'-bis(thymine)ferrocene nucleoside is reported. This molecule was obtained in a two-step synthetic methodology including a Michael addition reaction of 1, 1'-bis(3-chloropropionyl)ferrocene with thymine as a first step. In the 2nd step, the two prochiral carbonyl functionalities in the Michael adduct were reduced to hydroxyl functionalities. Reduction proceeds in a highly stereoselective fashion, yielding the ferrocenyl nucleoside as a racemic mixture consisting of the (R, R) and the (S, S) isomers. The absolute configuration at the chiral carbon atoms was unambiguously confirmed by single-crystal X-ray diffraction analysis for the methyl derivative of the nucleoside. The mechanism of reduction was investigated with DFT calculations. The two critical minima, prereactive complex and semi-reduced intermediate, and two corresponding transition states were located in support of the observed diastereoselectivity. The redox properties of 1, 1'-bis(thymine)ferrocene nucleoside, its precursor and congeners were investigated using cyclic voltammetry.

organometallic chemistry, electrochemistry, bioactive compounds, reaction mechanism, DFT

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