Heck RF.
Research Center of Hercules Inc., Wilmington, USA
Arylation, Methylation, and Carboxyalkylation of Olefins by Group VIII Metal Derivatives.
J. Am. Chem. Soc. 1968;
90: 5518-5526
DOI:
10.1021/ja01022a034
Key words
Heck reaction - palladium catalysis - C–C bond formation
Significance
Controllable and predictable C–C bond formation in organic chemistry is of paramount
importance. The early work by Heck on the addition of organometallic (organomercury,
organotin) compounds to olefins catalyzed by palladium(II) salts revolutionized how
retrosynthetic disconnections could be made. These results, along with additional
reports by Mizoroki and others, paved the way for the development of future transition
metal C–C bond forming reactions.
Comment
The author notes that palladium(II) salts exhibit the greatest performance when compared
to rhodium, ruthenium, nickel or iron salts. Additionally, more substituents on the
alkene coupling partner led to a decrease in the reactivity. It was reported that
electron donating substituents on the organometallic reagent decreased the yields,
with strongly coordinating amino groups completely inhibiting reactivity. This outcome
may be due to the formation of catalytically inactive complexes with the palladium.
When unsymmetrical alkenes are used, the addition of the organometallic species occurs
on the less substituted carbon atom.
