Palladium- (and nickel-) catalyzed vinylation of aryl halides

Abstract

Functionalized styrenes are extremely useful building blocks for organic synthesis and for functional polymers. One of the most general syntheses of styrenes involves the combination of an aryl halide with a vinyl organometallic reagent under catalysis by palladium or nickel complexes. This Feature Article provides the first comprehensive summary of the vinylation methods currently available along with a critical comparison of the efficiency, cost and scope of the methods.

Nickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen Bonds

“…Styrene derivatives are important monomers and building blocks for fine chemical and their synthesis by vinylation of aryl halides using Pd vs Ni-cross-coupling was recently reviewed by Denmark 251. Two general strategies are employed for the synthesis of styrene derivatives the first one by cross-coupling of vinyl electrophiles with aryl zinc reagents or by cross-coupling of aryl electrophiles with vinyl zinc reagents.…”

Silver-mediated fluorination of aryl silanes

“…Aryl silane derivatives have been used in catalysis, 9 for example in the Hiyama reaction––the Pd- or Ni-catalyzed cross-coupling reaction of organosilanes with organohalides or -triflates. 10 Silver(I) oxide (Ag 2 O) has been used by Hiyama and others as an activator for aryl silanols that undergo Pd-catalyzed biaryl formation.…”

Retracted article: Cross coupling in water: Suzuki–Miyaura vinylation and difluorovinylation of arylboronic acids

“…A second and different aryl group can be easily added by repeating the coupling protocol with the isolated and purified monarylated alkenes ArClC=CF 2 . The respective ArAr¢C=CF 2 products are isolated in excellent yields over the two steps (Table 4, entries 8,9).…”