146767-38-6Relevant articles and documents
α-Arylation of Ketones via the Reaction of Silyl Enol Ethers with Arenediazonium Salts
Sakakura, Toshiyasu,Hara, Masayasu,Tanaka, Masato
, p. 1545 - 1546 (1985)
The reaction of the silyl enol ethers of aryl ketones with arenediazonium salts gives α-arylated ketones in good yields under mild conditions.
Combined Theoretical and Experimental Studies Unravel Multiple Pathways to Convergent Asymmetric Hydrogenation of Enamides
Yang, Jianping,Massaro, Luca,Krajangsri, Suppachai,Singh, Thishana,Su, Hao,Silvi, Emanuele,Ponra, Sudipta,Eriksson, Lars,Ahlquist, M?rten S. G.,Andersson, Pher G.
supporting information, p. 21594 - 21603 (2021/12/27)
We present a highly efficient convergent asymmetric hydrogenation of E/Z mixtures of enamides catalyzed by N,P-iridium complexes supported by mechanistic studies. It was found that reduction of the olefinic isomers (E and Z geometries) produces chiral amides with the same absolute configuration (enantioconvergent hydrogenation). This allowed the hydrogenation of a wide range of E/Z mixtures of trisubstituted enamides with excellent enantioselectivity (up to 99% ee). A detailed mechanistic study using deuterium labeling and kinetic experiments revealed two different pathways for the observed enantioconvergence. For α-aryl enamides, fast isomerization of the double bond takes place, and the overall process results in kinetic resolution of the two isomers. For α-alkyl enamides, no double bond isomerization is detected, and competition experiments suggested that substrate chelation is responsible for the enantioconvergent stereochemical outcome. DFT calculations were performed to predict the correct absolute configuration of the products and strengthen the proposed mechanism of the iridium-catalyzed isomerization pathway.
Diarylated ethanones from Mo(CO)6-mediated and microwave-assisted palladium-catalysed carbonylative Negishi cross-couplings
Motwani, Hitesh V.,Larhed, Mats
supporting information, p. 4729 - 4733 (2013/08/23)
Two protocols for palladium-catalysed carbonylative Negishi cross-couplings were developed for aryl iodides and aryl bromides. The two main breakthroughs were that molybdenum hexacarbonyl [Mo(CO)6] could be used as a solid in situ source of CO, and that controlled microwave irraditaion could be used for heating. Consequently, the reactions were safe (in contrast to when CO gas was used) and fast (in comparison to when conventional heating was used). The carbonylative cross-coupling reactions were carried out using commercially available benzylzinc bromide in closed vials (90-120°C for 0.5-1 h) to give a set of diarylated ethanones, a common pharmacophore found in several pharmaceuticals, in moderate to high isolated yields (47-84 %). The mild three-component carbonylation protocol presented here is operationally simple, safe, and rapid, and the formation of the carbonylative Negishi cross-coupling product is favoured over the product of Negishi cross-coupling. Copyright
