Palladium-Induced Intramolecular Coupling Reactions of Some Alkenyl(o-iodobenzyl)silanes

Construction of Benzosiloles, Six- and Eight-Membered Silacyclic Skeletons, via a Pd-Catalyzed Intramolecular Mizoroki–Heck Reaction of Vinylsilanes

“…However, it is rarely reported that vinylsilane participates in the Mizoroki–Heck reaction. , Among all those examples reported on intermolecular Mizoroki–Heck reactions, formation of new C–C bonds at the β-position of vinylsilane is predominate . To the best of our knowledge, there is only one example of the formation of a C–C bond at the α-position of vinylsilane . Meanwhile, this is also the only report of an intramolecular Mizoroki–Heck reaction leading to a five-membered silacyclic ring as a byproduct in <30% yield …”

“…Vinyl silane is an important building block for constructing C–C bonds along with desilylation of the remaining silyl moiety. − As shown in Scheme , vinylsilanes have been used in the Hiyama cross-coupling reaction to make C–C bonds using the silyl group as a leaving group . Conceptually, the Mizoroki–Heck reaction is a good choice to make C–C bonds while the silyl group remains in the product. ,, Thus, silacyclic skeletons can be constructed via an intramolecular Mizoroki–Heck reaction of vinylsilanes (Scheme ) . However, it is rarely reported that vinylsilane participates in the Mizoroki–Heck reaction. , Among all those examples reported on intermolecular Mizoroki–Heck reactions, formation of new C–C bonds at the β-position of vinylsilane is predominate .…”

“…Conceptually, the Mizoroki–Heck reaction is a good choice to make C–C bonds while the silyl group remains in the product. ,, Thus, silacyclic skeletons can be constructed via an intramolecular Mizoroki–Heck reaction of vinylsilanes (Scheme ) . However, it is rarely reported that vinylsilane participates in the Mizoroki–Heck reaction. , Among all those examples reported on intermolecular Mizoroki–Heck reactions, formation of new C–C bonds at the β-position of vinylsilane is predominate . To the best of our knowledge, there is only one example of the formation of a C–C bond at the α-position of vinylsilane .…”

Selective synthesis of (E)-triethyl(2-arylethenyl)silane derivatives by reaction of aryl bromides with triethyl vinylsilane catalysed by a palladium–tetraphosphine complex

“…Similar reaction rates were obtained with electron-rich and electron-poor aryl bromide. For example, turnover numbers of 7500-10,000 can be achieved with this catalyst for activated substrates such as 4-bromoacetophenone, 4-bromobenzaldehyde, 4-bromobenzophenone, 4-bromobenzonitrile and 4-fluorobromobenzene ( Table 2, entries [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. With the deactivated aryl bromides: 4-t butylbromobenzene, 4-bromoanisole and 4-dimethylaminobromobenzene TONs of 5600, 7400 and 1000 were obtained, respectively ( Table 2, entries 24-27 and 30).…”

“…Few ligands have been successfully employed for the reaction in the presence of these alkenes. The most popular one is triphenylphosphine but the palladium complexes formed with this ligand are generally not very efficient in terms of substrate/catalyst ratio, moreover, this catalyst was used in most cases with very reactive but expensive aryl iodides [3][4][5][6][7][8][9]. Tri-2-furylphosphine ligand in the presence of 2.5-5% Pd 2 (dba) 3 also catalyses the reaction of aryl iodides with 2-pyridyldimethyl(vinyl)silane [10,11].…”