NICKEL-TRANSFER-CATALYZED AND PHASE-TRANSFER-CATALYZED CARBOXYLATION OF PROPARGYL AND ALLENYL HALIDES

Propargyl and allenyl halides are carbonylated in the presence of Ni(CN)2 under phase-transfer conditions (4-methyl-2-pentanone, 5 N NaOH, tetraalkylammonium halide) at room temperature or slightly above and atmospheric pressure of CO to give allenic monoacids or unsaturated diacids with high regio-...

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Published inOrganometallics Vol. 12; no. 5; pp. 1871 - 1875
Main Authors ARZOUMANIAN, H, COCHINI, F, NUEL, D, ROSAS, N
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 01.05.1993
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
CARBONYLATION
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Summary:Propargyl and allenyl halides are carbonylated in the presence of Ni(CN)2 under phase-transfer conditions (4-methyl-2-pentanone, 5 N NaOH, tetraalkylammonium halide) at room temperature or slightly above and atmospheric pressure of CO to give allenic monoacids or unsaturated diacids with high regio- and stereoselectivities. It is shown that the monoacid is first obtained followed by a slower second carbonylation. Propargyl halides react catalytically whereas allenyl halides necessitate the presence of excess KCN. This is rationalized in terms of two different mechanisms; in the former case, the nickel catalyst plays the role of a true nucleophile, and in the latter the nickel center undergoes an oxidative addition/reductive elimination sequence facilitated by the high trans influence of cyano groups.
ISSN:0276-7333
DOI:10.1021/om00029a049