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Synthesis 2003(12): 1787-1789
DOI: 10.1055/s-2003-41032
SHORTPAPER
© Georg ThiemeVerlag Stuttgart · New York

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

Karl Heinz Dötz*, Edite Gomes da Silva
Kekulé-Institut für OrganischeChemie und Biochemie , Rheinische Friedrich-Wilhelms-Universität, 53121 Bonn, Germany
Fax: +49(228)735813; e-Mail: E-mail: doetz@uni-bonn.de;
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Publication History

Received 12 July 2003
Publication Date:
13 August 2003 (online)

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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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1

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]