Organometallic NucleosideAnalogues: An Adenine-Analogue Fischer Carbene­ Complex [1]

Abstract

A six-step synthesis of a nucleoside analogue Fischer carbenecomplex has been developed starting from d-ribono-1,4-lactone.The key steps involve a stoichiometric metathesis of exo-glycal 3 withpentacarbonyl[(diphenyl)carbene]chromium to give chromiumfuranosylidene 4, its ring-opening aminolysiswith the nucleobase adenine and a Mitsunobu recyclisation leadingto imino-l-lyxo-furanosylidene complex 6 with inversion of configuration.

Key words

carbene complexes - carbohydrates - chromiumcomplexes - glycosylidene complexes - nucleosides

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Organotransition metal modified sugarsPart 28 For Part 27 see: Dötz, K. H.; Gomes da Silva E. J. Organomet. Chem. 2003,in press.

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Organotransition metal modified sugarsPart 28 For Part 27 see: Dötz, K. H.; Gomes da Silva E. J. Organomet. Chem. 2003,in press.

9

IR-Absorptions of pentacarbonyl(diphenylcarbene)chro-mium:2062 (m), 1977 (s), 1960 (vs) cm^-1

15

UV-irradiation of iminofuranosylidenecomplex 6 in MeOH with a 500 W sunlampresulted in a modest yield (10%) of methyl 2,5-adenino-6-O-benzyl-2,5-dideoxy-3,4-O-isopropylidene-l-lyxonate.A single set of NMR-signals (including ³ J _H-2/H-3 = 8.04Hz indicative of a trans vicinal couplingconstant) suggests a diastereoselective formation of the β-C-iminoglycoside as previously observedunder similar conditions for the pyranose series. [13a]