Hiyama cross-coupling reaction, palladium

Fluoride-free Hiyama cross-coupling reactions of phenyltrimethoxysilane with aryl halides was performed in water using sodium hydroxide as activator at 110°C under microwave heating [32]. The reaction was catalyzed by poly (N-viityl-2-pyrrolidone) (PVP)-stabilized colloidal palladium NPs. The reaction proceeds quickly under microwave heating (6 min). 

The palladium-catalyzed reaction of alkenyl-, aryl-, alkynyl- and alkylsiloxanes with aryl, alkyl, and alkenyl halides and triflates in the presence of activators is known as the Hiyama cross-coupling reaction and several reviews have been published. This chapter will present major developments and examples of recent carbon-carbon bond formation methodology and improvements as well as their use in natural products synthesis in the last few years. 

A colloidal palladium nanoparticle prepared from a Fischer carbene complex of tungsten with K2PdCl4 as the reductant and PEG as the capping agent, efficiently catalyzed the Hiyama cross-coupling reactions in air. ... 

Shah and Kaur (2012) reported a nonfunctional macroporous commercial resin, Amberlite XAD-4, impregnated with palladium nanoparticles (PdNPs) of size 5-10 nm. These supported Pd nanoparticles were used to catalyze the sodium hydroxide activated Hiyama cross-coupling reaction of phenyltrimethoxysilane with a variety of bromo and chloroarenes under microwave heating. These were found to have... 

The C-C bond forming reaction of an organic halide with an organosilane, catalysed by nickel or palladium, is known as the Hiyama cross-coupling. Typically the C-Si bond needs to be activated by either electronegative substituents or by external fluoride anions. 

Cross-coupling reactions 5-alkenylboron boron compounds, 9, 208 with alkenylpalladium(II) complexes, 8, 280 5-alkylboron boron, 9, 206 in alkyne C-H activations, 10, 157 5-alkynylboron compounds, 9, 212 5-allylboron compounds, 9, 212 allystannanes, 3, 840 for aryl and alkenyl ethers via copper catalysts, 10, 650 via palladium catalysts, 10, 654 5-arylboron boron compounds, 9, 208 with bis(alkoxide)titanium alkyne complexes, 4, 276 carbonyls and imines, 11, 66 in catalytic C-F activation, 1, 737, 1, 748 for C-C bond formation Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 via Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 via Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 for C-H activation, 10, 116-117 for C-N bonds via amination, 10, 706 diborons, 9, 167... 

Tsuji-Trost allylation reactions offer multiple pathways to tetrahydrofuran synthesis including C-C bond-formation steps. A palladium-catalyzed sequence of allylic alkylation and Hiyama cross-coupling provides a convenient synthesis of 4-(styryl)-lactones (Scheme 67) <2006SL2231>. 

Shimizu and Hiyama [129] reported that the palladium-catalyzed double-cross-coupling reaction of 9-stannafluorenes 213 with 1,1-dihaloethylene 214 yields the dibenzofulvene 215 (Scheme 6.57a). The 9-staimafluorene 213, an equivalent of a 1,4-dimetalated reagent, is available from the corresponding 2,2 -dihalobiphenyls. The reaction was applied to the synthesis of the jt-extended fulvalene derivative 217 from 216. The former is a stable benzaimulated Chichibabin hydrocarbon possessing an open-shell diradical character (Scheme 6.57b) [130]. 

Palladium catalysed Hiyama-type cross-coupling reactions of benzylic phosphates (74) with the aryl-silane (75) afforded corresponding di-arylmethanes (76) (Scheme 21). The reaction tolerated either electron-donating or electron-withdrawing functional groups providing products (76) in high to excellent yields. ... 

At this point, it should be noted that the Sanford group isolated an aryl-trifIuoromethyl-palladium(IV) complex that undergoes reductive elimination to yield benzotrifluorides. Pyridylsilanes can efficiently be used as starters for Hiyama crosscoupling reactions if a copper co-catalyst is used (Experimental Procedure below, a general procedure for Hiyama cross-coupling of pyridylsilanes). ... 

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