Nucleic acid related compounds. 78. Stereocontrolled syntheses of 6′(E and Z)-halovinyl analogues from uridine-derived vinylsulfones via vinyltin intermediates

Abstract

Treatment of the 6′(E)-tosylvinyl homonucleoside 1a with Bu3SnH/AIBN/toluene/Δ gave separable mixtures of 6′-vinylstannanes 2a(E/Z) in high yields. Stereospecific halodestannylations with N-iodosuccinimide, bromine, and N-bromosuccinimide proceeded smoothly to give the 6′(E or Z)-iodo(and bromo) vinyl compounds with retention of configuration. Chlorine or iodobenzene dichloride effected moderately stereoselective chlorodestannylation. Treatment of 2a with NH4F/MeOH/Δ resulted in carbon–tin bond cleavage to give the free vinyl derivative 4a. Aqueous trifluoroacetic acid effected concomitant protiodestannylation and deprotection of 2a to give 4b. Treatment of 2a(E) with lead tetraacetate/acetonitrile and deprotection afforded acetylenic derivative 3b.