631898-31-2

Upstream product

• 89756-88-7 1,3-bis(diphenylphosphinomethyl)benzene 
• 109-99-9 tetrahydrofuran 
• 626-16-4 3-(chloromethyl)benzyl chloride 
• 829-85-6 diphenylphosphane 

Downstream Products

• 866367-18-2 [(C₆H₃(CH₂P(C₆H₅)2)2)Pd(CH₃)] 
• 89770-77-4 (2,6-bis[(diphenylphosphino)methyl]phenyl)bromopalladium 
• 866367-21-7 [(C₆H₃(CH₂P(C₆H₅)2)2)Pd(C₆H₅)] 

Relevant academic research and scientific papers

The first synthesis of stable palladium(II) PCP-type catalysts supported on silica - Application to the heck reaction

An efficient method for the formation of a silica-immobilized tridentate diphosphinoaryl ligand (PCP-type) palladium(II) complex (11) is described and successfully used as a catalyst for the Heck reaction. Commercially available 5-amino-isophthalic acid dimethyl ester was converted to N-acetyl-3,5-bis(chloromethyl)aniline (4) in three steps, by reduction, acetylation, and chlorination (Scheme 1). Arbuzov reaction of 4 led to the diphosphine oxide (5). Deprotection and functional group manipulations allowed the transformation of 5 into N-[3,5-bis-(diphenyl-phosphinoylmethyl)-phenyl]-succinamic acid (7). Subsequent reduction of 7 with HSiCl3 afforded the diphosphine (8) attached to silica by transforming compound 8 to N-{3,5-bis[(diphenyl-phosphanyl)methyl]-phenyl}-succinamic acid 2,5-dioxo-pyrrolidin-1-yl ester (9). Palladium(II) trifluoroacetate was used to form the PCP-type palladium(II) complex. This complex shows high catalytic activity in the Heck reaction for aryl iodides, and it is also active with aryl bromides. The catalyst is thermally stable and it is also stable towards oxygen and moisture. In addition, it can be recycled by simple filtration in air and reused with moderate loss of activity.

A catalytic and mechanistic investigation of a PCP pincer palladium complex in the Stille reaction

In an improved procedure, the complex {2,6-bis[(diphenylphosphino)methyl] benzene}chloropalladium(II) (1) was synthesised as its THF adduct and the structure was determined by X-ray crystallography. The catalytic properties of the derivative {2,6-bis[(diphenylphosphino)methyl]benzene}(trmuoroacetato) palladium(II) (2) was investigated in the Stille reaction. Complex 2 proves to be an excellent catalyst for the C-C cross-coupling between trimethyl phenyl stannane and aryl bromides using a very low catalyst loading (0.1-0.0001%), giving high turnover numbers (TONs) up to 6.9 × 105. A kinetic investigation of the catalytic reaction suggests a heterogeneous colloidal palladium catalyst formed from the PCP Pd(II) pre-catalyst. The Royal Society of Chemistry 2005.

Insertion of carbon dioxide into (PCP)PdII-Me bonds

A (PCP)PdMe complex has been synthesized and structurally characterized, displaying a very long Pd-Me bond. It is reactive toward CO2 insertion, giving the corresponding acetate in quantitative yield. The methyl complex can be regenerated using ZnMe2, and catalytic carboxylation is possible in benzene.