Expanding the borononucleotide family: synthesis of borono-analogues of dCMP, dGMP and dAMP.

Anthony R. Martin (1) , Kishor Mohanan (1) , Delphine Luvino (1) , Nicolas Floquet (1) , Carine Baraguey (1) , Michaël Smietana (1) , Jean-Jacques Vasseur (1)

1 IBMM - Institut des Biomolécules Max Mousseron [Pôle Chimie Balard]

We previously reported the synthesis of a borononucleotide analogue of thymidine monophosphate and its association towards the formation of a new borono-linked dinucleotide. Here we describe the completion of the set of four 2′-deoxyborononucleotide analogues of natural nucleotide monophosphates, namely the previously unknown dCbn, dGbn and dAbn. These analogues were all prepared from the respective 5′-aldehydic nucleosides through a homologation/reduction sequence. The borononucleotides were subsequently obtained by either borylation (dCbn and dGbn) or cross-metathesis (CM) in the presence of the Hoveyda–Grubbs catalyst (dAbn). The reversible formation of the corresponding dinucleotides between these new analogues and uridine was studied by 1H NMR, and semi-empirical calculations were carried out to provide bond length and electrostatic information that assess the structural similarities existing between these bioisosteres and their natural counterparts.

Domaines: Chimie organique

Anthony R. Martin, Kishor Mohanan, Delphine Luvino, Nicolas Floquet, Carine Baraguey, et al.. Expanding the borononucleotide family: synthesis of borono-analogues of dCMP, dGMP and dAMP.. Organic & Biomolecular Chemistry, 2009, 7 (21), pp.4369-4377. ⟨10.1039/b912616c⟩. ⟨hal-01109915⟩