Alkynyl phosphorodithioates

The reactions of potassium thiotosylate and potassium 0,0-dialkyl phospho-rodithioates with alkynyl(phenyl)iodonium salts afford good yields of alkynyl thiotosy-lates and alkynyl phosphorodithioates (equations 63 and 64)87,. Cyclopentenyl products have not been reported in either case. 

The reaction of ArS(0)2SK [67] and (R 0)2PS2K [68] with alkynyliodonium salts results in alkynyl thiotosylates, 85, and alkynyl phosphorodithioates, 86, respectively [Eqs. (42), (43)] in good isolated yields. Interaction of thiocarboxylates, 87, with alkynyliodonium triflates gives the hitherto unknown alkynyl thiocarboxylates, 88 [Eq. (44)] [69]. 

Alkynyl thiocyanates Alkynyl thiotosylates Alkynyl phosphorodithioates... 

The alkynylation of sulfur nucleophiles works well with alkynyliodonium tosylates and triflates as long as the sulfur atom is not too electron-rich, else oxidation reactions dominate. For example, alkynyl thiocyanates [38, 39, 75], thiotosylates [76], and phosphorodithioates [77] can be accessed in good yields (Scheme 8, A). The alkynylation of thioamides is also possible, but in this case the product obtained is imstable and spontaneously cyclizes to give a thiazole (Scheme 8, B) [78, 79]. The alkynylation of sulfinates with alkynyliodOTiium triflates or tosylates gives an efficient access towards alkynyl sulfones (Scheme 8, C) [80, 81]. If C-H bonds are easily accessible, carbene C-H insertion products can... 

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