ORGANIC-CHEMISTRY IN WATER .5. NUCLEOPHILIC-ADDITION OF WATER-SOLUBLE PHOSPHINES ON ACTIVATED ALKYNES - AN EFFICIENT SYNTHESIS OF NEW VINYLPHOSPHONIUM SALTS AND OF SPECIFICALLY DEUTERATED OLEFINS

Triphenylphosphinc m-trisulfonate [P(mC6H4S03Na)3 =TPPTS]1 and triphenylphosphine m-monosulfonate [Ph2P(mC6H4SO3Na)=TPPMS]2 react in water with activated alkynes R-C s C-A (A = CO2H, CO2Rl, COR2, CHO) affording new vinylphosphonium salts or vinylphosphine oxides or alkenes depending on the pH of the aqueous solution and on the nature of the substituent R. The reactions of 1 or 2 with alkynes bearing an electron-acceptor substituent R give rise to the corresponding trans disubstituted olefins. Specifically mono or dideuterated alkenes are thus obtained in good yields by sequential use of H2O-D2O. When R = H or Alkyl, vinylphosphonium salts or vinylphosphine oxides are quantitatively produced respectively in acidic or in neutral medium. © 1990.