In 2019,Journal of the American Chemical Society included an article by Reddi, Yernaidu; Tsai, Cheng-Che; Avila, Carolina M.; Toste, F. Dean; Sunoj, Raghavan B.. Quality Control of Tris(dibenzylideneacetone)dipalladium(0). The article was titled 《Harnessing Noncovalent Interactions in Dual-Catalytic Enantioselective Heck-Matsuda Arylation》. The information in the text is summarized as follows:
The use of more than one catalyst in one-pot reaction conditions has become a rapidly evolving protocol in the development of asym. catalysis. The lack of mol. insights on the mechanism and enantioselectivity in dual-catalytic reactions motivated the present study focusing on an important catalytic asym. Heck-Matsuda cross-coupling. A comprehensive d. functional theory (M06 and B3LYP-D3) investigation of the coupling between a spirocyclic cyclopentene and 4-fluorophenyl diazonium species under a dual-catalytic condition involving Pd2(dba)3 (dba = trans,trans-dibenzylideneacetone) and chiral 2,2′-binaphthyl diamine (BINAM)-derived phosphoric acids (BDPA, 2,2′-binaphthyl diamine-derived phosphoric acids) is presented. Among various mechanistic possibilities examined, the pathway with explicit inclusion of the base (in situ generated sodium bicarbonate/sodium biphosphate) is found to be energetically more preferred over the analogous base-free routes. The chiral phosphate generated by the action of sodium carbonate on BDPA is found to remain associated with the reaction site as a counterion. The initial oxidative addition of Pd(0) to the aryl diazonium bond gives rise to a Pd-aryl intermediate, which then goes through the enantiocontrolling migratory insertion to the cyclic alkene, leading to an arylated cycloalkene intermediate. Insights on how a series of noncovalent interactions, such as C-H···O, C-H···N, C-H···F, C-H···π, lp···π, O-H···π, and C-F···π, in the enantiocontrolling transition state (TS) render the migration of the Pd-aryl to the si prochiral face of the cyclic alkene more preferred over that to the re face are utilized for modulating the enantioselectivity. Aided by mol. insights on the enantiocontrolling transition states, we predicted improved enantioselectivity from 37% to 89% by changes in the N-aryl substituents of the catalyst. Subsequent experiments in our laboratory offered very good agreement with the predicted enantioselectivities. The experimental process involved the reaction of Tris(dibenzylideneacetone)dipalladium(0)(cas: 51364-51-3Quality Control of Tris(dibenzylideneacetone)dipalladium(0))
Tris(dibenzylideneacetone)dipalladium(0)(cas: 51364-51-3) is the most widely used PdO precursor complex in synthesis and catalysis, in particular as a catalyst for various coupling reactions. Quality Control of Tris(dibenzylideneacetone)dipalladium(0) It is used as a catalyst precursor for palladium-catalyzed carbon-nitrogen bond formation, conversion of aryl chlorides, triflates and nonaflates to nitroaromatics.
Referemce:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI