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Synlett 2010(15): 2251-2256  
DOI: 10.1055/s-0030-1258038
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Facile Synthesis of Novel Acyclo-C-Nucleoside Analogues from l-Rhamnose via Variants of Bohlmann-Rahtz Reaction

Srinivas Kantevari*, Siddamal Reddy Putapatri
Organic Chemistry Division-II, Indian Institute of Chemical Technology, Hyderabad 500007, India
e-Mail: kantevari@yahoo.com; e-Mail: kantevari@gmail.com;
Further Information

Publication History

Received 9 June 2010
Publication Date:
12 August 2010 (online)

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Abstract

Synthesis of a series of novel acyclo-C-nucleoside analogues bearing substituted pyridines, dihydro-6H-quinolin-5-ones, dihydro-5H-cyclopentapyridin-5-one, tetrahydrocyclohepta[b] pyr­idine-5-one, and azafluorinone has been achieved in very good yields, through CeCl3˙7H2O-NaI-catalyzed one-pot condensation of a variant of the Bohlmann-Rahtz reaction using β-enaminones derived from l-rhamnose, acyclic and cyclic 1,3-dicarbonyls, and ammonium acetate. Ready availability of reactive β-enaminones, use of a cerium catalyst, and shorter reaction times are the advantages of this protocol over previous methodology. A plausible mechanism invoking cerium-catalyzed sequential Michael addition-cyclode­hydration-elimination reactions is also presented.

Key words

Bohlmann-Rahtz reaction - acyclo-C-nucleosides - CeCl3˙7H2O-NaI - one-pot condensation - β-enaminone - l-rhamnose - heterocycles

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We thank one of the referees for suggesting conjugated dihydropyridine intermediate in the mechanistic sequence in Scheme  [³] .