Sulfur and selenium derivatives of 2-phosphaindolizines

The 2-phosphaindolizines 1 react with hydrogen sulfide and elemental sulfur to give the new zwitterionic heterocyclic systems 2 of the N-pyridiniomethyl dithiophosphinate type. In contrast, no reaction is observed with sulfur alone. MeI methylates 2e,f at sulfur. The analogous pyridiniodiselenophosphinate 5 results from the reaction of 1a with 1,3,2,4-diselenadiphosphetane-2,4-diselenide, 4a, in the absence of an additional base. As a further product, the perselenophosphinic anhydride 6 is identified. In the presence of triethylamine, 1a reacts with each of the diselenides 4a–c to give the new triethylammonium diselenophosphinates 7a–c, respectively. This reaction can be extended to 1-aza-2-phosphaindolizine, 8, which yields with each of 4a,b and NEt₃ the diselenophosphinates 9a,b, respectively. The anhydride 6 and the diselenophosphinates 7 and 9 result from an electrophilic substitution at the phosphaindolizine ring. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:445–452, 1998