D- and L-carbocyclic nucleosides were obtained by a new procedure involving an enantioselective rhodium/duphos-catalyzed hydroacylation reaction as the key step. The 3-hydroxymethyl-cyclopentanol intermediate was obtained by stereoselective reduction of ketone and by dynamic kinetic resolution (DKR).
This methodology is particularly useful for the direct synthesis of primary and N-methyl amides using urea as a stable and easy to manipulate nitrogen source.
The catalytic meta-functionalization of arenes has emerged as important synthetic methodology in the last decade. We report herein structural and mechanistic studies of the meta-sulfonation of phenylpyridine using ruthenium complexes.Furthermore, we disclose that the catalytically active species does not require the presence of a -arene ligand.Furthermore, the novel cycloruthenated phenylpyridine complex tosylated at the para position to the metal has been isolated and fully characterised. Protodemetallation studies suggest that a concerted C-H activation-demetallation process may be involved. Overall, this study provides fundamental insight into the meta-sulfonation phenylpyridine reaction pathway and uncovers new reaction intermediates that will guide the design of new catalytic systems for remote metafunctionalization.
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