58838-13-4Relevant articles and documents
RHODIUM CATALYZED HYDROACYLATION OF ETHYLENE WITH 4-PENTENALS. REACTIONS OF 4-HEXENAL-1-d
Vora, Krishnakant P.,Lochow, Charles F.,Miller, Roy G.
, p. 257 - 264 (1980)
A catalyst derived from 2,4-pentanedionatobis(ethylene)rhodium(I), I, promoted the addition of 4-pentenal to ethylene.The reaction was accompanied by the formation of double bond migration products derived from the 4-pentenal reactant and from the 6-hepten-3-one primary product.Compound I accomplished the addition of 4-hexenal to ethylene to afford high yields of 6-octen-3-one.The fate of the aldehyde hydrogen in this transformation has been determined in experiments employing 4-hexenal-1-d as reactant.Treatment of 4-hexenal-1-d with I in CHCl3 and CDCl3 afforded 6-octen-3-one possesing > 50percent d0 molecules while the isotopic composition of recovered unexpended 4-hexenal remained > 96percent d1. 6-Octen-3-one products with isotopic compositions of > 66percent d0 were afforded when ethylene was introduced to reaction mixtures.The location of deuterium in 6-octen-3-one, derived from treatment of 4-hexenal-1-d with I in the absence of added C2H4, was determined to be distributed at C-1 and C-2 and at the C=C bond by analysis of the 1H and 2H NMR spectra.Unexpended ethylene was recovered and was found to contain a substantial amount of deuterium.Mechanistic implications of these results are discussed.
