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Abstract

The vitamin-B 12 derivative 11, incorporating a peripheral N 4 -acetylcytosine moiety, was alkylated under reductive conditions with 2-(iodomethyl)-2-methylmonothiomalonate 8 bearing the complementary guanine moiety. The reaction yielded a mixture of vitamin-B 12 -derived complexes with variations in the cytosine moiety: products 16 ± 18 with a cytosine, a N 4 -acetylated cytosine, and a N 4 -acetylated reduced cytosine moiety were formed (see Scheme 5). The complexes were photolyzed in CHCl 3 /MeCN to yield the dimethylmalonate derivative 22 (Scheme 6) but not the rearranged succinate, in contrast to the results obtained earlier with complexes incorporating the A ¥ T base pair (see Scheme 1).

Synthesis of 5‐/8‐Halogenated or Ethynylated Lipophilic Nucleobases as Potential Synthetic Intermediates for Supramolec­ular Chemistry

“…To circumvent these problems, substitution of the 6-chloro atom with a 2-trimethylsilylethoxy group [29] was next considered with the aim of reducing the reactivity of such position in the halogenation step. This particular protecting group was chosen because of several additional advantages in the synthetic route: it imparts solubility to the heterocyclic ring and can be efficiently deprotected in the presence of fluoride at the very last step in the route, [30] along with the TMSA group.…”

Chemistry and Enzymology of Vitamin B12

“…The model was completed by Sun and Darbre, who synthesized the organocobalt derivatives 29 − 31 from 28 . These complexes have an organic ligand with a dimethylmalonate-like group (which models the substrate for the methylmalonylCoA mutase reaction) bound to cobalt via the carbon analogous to the radical-bearing carbon of the methylmalonylCoA mutase reaction and also tethered to a guanine residue to allow G−C base pairing to hold the “substrate” radical formed by photolysis in the proximity of the metal.…”

Synthesis and in vitro activity of platinum containing 2-oxazoline-based glycopolymers

“…In the same manner, it is possible to incorporate anticancer active units by photoaddition of tpy‐thiols (tpy‐SH) and subsequent platinum complexation. Tpy‐thiols are described in literature but have not been attached to POx so far . Here we describe the synthesis of Pt(II) containing, water soluble, 2‐oxazoline based glycopolymers.…”