52095-40-6Relevant articles and documents
Intramolecular One-Carbon Homologation of Unstrained Ketones via C-C Activation-Enabled 1,1-Insertion of Alkenes
Huang, Jiangkun,Zhang, Rui,Wu, Xiuli,Dong, Guangbin,Xia, Ying
, p. 2436 - 2440 (2022/04/07)
Here, we describe the development of a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a distinct approach to access various substituted 1-indanones. Computational mechanistic studies reveal that the formal 1,1-insertion is realized by a selective C(sp2)-C(sp3) activation and turnover limiting 2,1-insertion into the alkene, followed by a facile β-H elimination and reinsertion process.
Rhodium-Catalyzed Hydrocarboxylation of Olefins with Carbon Dioxide
Kawashima, Shingo,Aikawa, Kohsuke,Mikami, Koichi
, p. 3166 - 3170 (2016/07/19)
The catalytic hydrocarboxylation of styrenes derivatives and α,β-unsaturated carbonyl compounds with CO2(101.3 kPa) in the presence of an air-stable rhodium catalyst was explored. The combination of [RhCl(cod)]2(cod = cyclooctadiene) as a catalyst and diethylzinc as a hydride source allowed for effective hydrocarboxylation and provided the corresponding α-aryl carboxylic acids in moderate to excellent yields. In this catalytic process with carbon dioxide, intervention of the RhI–H species, which could be generated from the RhIcatalyst and diethylzinc, was clarified. Significantly, the catalytic asymmetric hydrocarboxylation of α,β-unsaturated esters with carbon dioxide was also performed by employing a cationic rhodium complex possessing (S)-(–)-4,4′-bi-1,3-benzodioxole-5,5′-diylbis(diphenylphosphine) [(S)-SEGPHOS] as a chiral diphosphine ligand. A plausible model for asymmetric induction was proposed by determination of the absolute configuration of the product.
One-pot Suzuki/Heck sequence for the synthesis of (E)-stilbenes featuring a recyclable silica-supported palladium catalyst via a multi-component reaction in 1,3-propanediol
Joucla, Lionel,Cusati, Giuseppe,Pinel, Catherine,Djakovitch, Laurent
scheme or table, p. 1993 - 2001 (2010/10/20)
The synthesis of (E)-stilbenes was performed following a one-pot Suzuki/Heck sequence through the use of potassium vinyltrifluoroborate. The combination of heterogeneous palladium/silica (Pd/SiO2) catalyst with potassium phosphate monohydrate (K3PO4?H 2O) as base resulted in useful to good isolated yields regardless of the ortho-, meta- or para-substitution of the aryl halides employed. In a sustainable approach, we found that bio-sourced 1,3- propanediol could advantageously replace N-methylpyrrolidone (NMP) as similar yields were obtained. Moreover, the reactivity gap between aryl iodides and bromides resulting from the use of 1,3-propanediol allowed an efficient multi-component approach toward the synthesis of (E)-stilbenes. Furthermore, this heterogeneous catalyst was found to be extremely robust despite the use of aerobic conditions and was successfully re-used over several cycles.