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.
