Fukuyama coupling

On the basis of this mechanism, it was surmised that substitution of Et3SiH by an appropriate organometallic reagent would provide access to ketones. Extensive screening of various transition metal catalysts and organometallic reagents have revealed suitable conditions, which are currently used in the Fukuyama-Coupling. 

The coupling of organozinc reagents with thioesters in the presence of palladium catalyst is known as the Fukuyama coupling. ... 

Fig. (33). Introduction of 4-carboxybutyl chani of 1 through the Fukuyama coupling reaction.

Tabic 11. Introducrion of 4-Carboxyb tyl Chain Through Fukuyama Coupling Reaction. 

Zinc dust was previously activated by the addition of carcinogenic 1,2-dibromoethane [0.026 equiv relative to zinc dust (Zn)] followed by chlorotrimethylsilane (TMSCl) (0.018 equiv relative to Zn), which gave rise to serious issues of poor reproducibility and requirement of excess iodide 80 (2.5 equiv relative to 8). Because the Fukuyama coupling reaction has been reported not to proceed with dialkyl zinc (R2Zn), the Schlenk equilibrium of the zinc reagent should lie to the left to achieve... 

Fig. (34). Schlenk equilibrium of zinc reagents and the utility for the Fukuyama coupling reaction.

A novel and practical synthesis of ( + )-biotin via the Fukuyama-coupling reaction 03YZ43. 

The acylpalladiums such as 138 are generated by oxidative addition of thioesters and used for ketone synthesis as reported by Fukuyama. Coupling of ethyl thioester of phenylalanine 137 with alkylzinc reagent 139 using P(o-Tol)3 as a ligand gave 140 in high yield [59], Phenyl thioesters are also used [60],... 

---