Stereoselective Addition of a Wittig Reagent To Give a Single Nucleoside Oxaphosphetane Diastereoisomer. Synthesis of 2′(and 3′)-Deoxy-2′(and 3′)-methyleneuridine (and cytidine) Derivatives from Uridine Ketonucleosides

Vicente Samano; Morris J. Robins

doi:10.1055/s-1991-26774

Synthesis 1991; 1991(4): 283-288
DOI: 10.1055/s-1991-26774

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Stereoselective Addition of a Wittig Reagent To Give a Single Nucleoside Oxaphosphetane Diastereoisomer. Synthesis of 2′(and 3′)-Deoxy-2′(and 3′)-methyleneuridine (and cytidine) Derivatives from Uridine Ketonucleosides

Vicente Samano^* , Morris J. Robins

^*Department of Chemistry, Brigham Young University, Provo, UT 84602, USA

Abstract

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Treatment of 3′,5′(or 2′,5′)-bis-O-silyl-protected 2′(or 3′)-ketouridine derivatives with methyltriphenylphosphonium bromide and sodium 2-methyl-2-butoxide in diethyl ether/benzene at 0-4°C resulted in the slow formation of the corresponding 2′(or 3′)-deoxy-2′(or 3′)-methylene analogues. ¹H- and ³¹P-NMR spectra were in harmony with formation of a single oxaphosphetane diastereoisomer during early stages of the Wittig reaction. Conversions of protected deoxymethyleneuridine to deoxymethylenecytidine derivatives were effected smoothly via 4-(1,2,4-triazol-1-yl) intermediates. Deprotection with tetrabutylammonium fluoride gave 2′(or 3′)-deoxy-2′(or 3′)-methyleneuridine and cytidine nucleosides.

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