ChemInform Abstract: Synthesis of (Z)-1-Organylthiobut-1-en-3-ynes: Hydrothiolation of Symmetrical and Unsymmetrical Buta-1,3-diynes

Hydrothiolation of 1-organylbuta-1,3-diynes and 1,4-di-organylbuta-1,3-diynes with the sodium organylthiolate anions,which were generated in situ by reacting diphenyl and dibutyl di-sulfide with NaBH 4 in ethanol, results in the regio-, stereo-, andchemoselective formation of ( Z )-1-organylthio-4-organylbut-1-en-3-ynes and ( Z )-1-organylthio-1,4-diorganylbut-1-en-3-ynes, re-spectively. Key words: hydrothiolation, organylthiolate anion, vinyl sulfides,1,3-diacetylenes, ( Z )-1-organylthiobut-1-en-3-ynes Vinyl sulfides are present in naturally occurring com-pounds with important biological activity. 1 Griseoviridin,for example, is a type A streptogramin antibiotic, first iso-lated from Streptomyces graminofaciens , 1a,b and benzyl-thiocrellidone is a yellow pigment isolated from thebright-red sponge Crella spinulata . 1c These compounds are versatile and useful intermediatesin organic synthesis. 2–13 They can be converted into thecorresponding aldehyde, ketone, 2 carboxylic acid, orester