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Rhodium catalyzed hydroacylation of ethylene with 4-pentenals. reactions of 4-hexenal-1-d

1980; Elsevier BV; Volume: 192; Issue: 2 Linguagem: Inglês

10.1016/s0022-328x(00)94430-9

1872-8561

Krishnakant P. Vora, Charles F. Lochow, Roy G. Miller,

Organometallic Complex Synthesis and Catalysis

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 possessing >50% do molecules while the isotopic composition of recovered unexpended 4-hexenal remained >96% d1. 6-Octen-3-one products with isotopic compositions of >66% do 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.