Application of palladium (trioxo-adamantyl cage phosphine)chloride complexes as catalysts for the alkoxycarbonylation of styrene; Pd catalysed tert-butoxycarbonylation of styrene

Pd-Catalyzed Regioselective Alkoxycarbonylation of 1-Alkenes Using a Lewis Acid [SnCl2 or Ti(OiPr)4] and a Phosphine

“…This acid-free condition was however encouraging because it indicated that the reaction could proceed under Brønsted acid free conditions when L1 is used as a ligand. This result also prompted us to consider another ketone-based solvent, 2butanone, which has been shown elsewhere 11 to be an effective cosolvent. Unfortunately, in this case, the results in 2-butanone also gave full conversion, with mediocre linear selectivity as well (Table 1, entry 5).…”

“…For example, in the palladium-phosphine catalyzed alkoxycarbonylation of styrene, the use of bidentate diphosphine ligands is known to furnish predominantly linear esters although some exceptions have also been found. Monodentate phosphine ligands on the other hand are widely known to give branched esters although Alper and co-workers showed that exceptional selectivity for linear esters of styrene can result using a monodentate phosphine…”

Efficient Palladium-Catalyzed Synthesis of 2-Aryl Propionic Acids

“…Here, palladium complexes in the presence of acid represent state-of-the-art catalyst systems for the synthesis of 2-aryl propionic acid. Recent catalyst developments in this area include the preparation of heterogeneous Pd-TPPTS complexes supported onto acidic resins [ 8 ] as well as homogenous systems such as-PdCl(allyl)(tri-oxo-adamantyl cage phosphines) [ 9 ], water-soluble Pd-TPPTS complexes [ 10 ], palladium(II) complexes containing naphthyl(diphenyl)-phosphine ligands [ 11 ] or bulky bidentate phosphines [ 12 ], and PdCl 2 (PPh 3 ) 2 /HCl/CO/THF in combination with heteropolyacids [ 13 ].…”

Hydroesterification of styrene derivatives catalyzed by an acidic resin supporting palladium complexes

“…It is especially worth mentioning that Pd complexes such as Pd(OTs) 2 (PPh 3 ) 2 and [Pd(MeCN) 2 (PPh 3 ) 2 ](BF 4 ) 2 , etc., are well-established for providing high activities and selectivities for the hydroesterification of olefins under mild conditions in a homogeneous system. 1b,5 Most recently, (PdCl(alkyl)(1,3,5,7tetramethyl-6-phenyl-2,4,8-trioxo-6-phospha-adamantane)) 6 has been reported as a highly regioselective catalyst in the hydroesterification of styrene. Although an outstanding catalytic activity and selectivity are exhibited in the homogenous system, there are serious issues regarding its practical utility due to difficulties in catalyst separation as well as reusability.…”