Facile preparation of aromatic ketones from aromatic bromides and arenes with aldehydes

Biaryl Ketones by Suzuki–Miyaura Cross‐Coupling of Organotrifluoroborates and Acyl Chlorides

“…13 C NMR (75 MHz, CDCl 3 ): δ = 199.48, 143.60, 137.45, 136.30, 134.13, 133.29, 128.72, 128.64, 127.41, 20.87, 20.28, 18.46 ppm. NMR spectra are consistent with previously reported data …”

Transition Metal‐Free Approach to Propynenitriles and 3‐Chloropropenenitriles

“…It also confirmed that formation of am ixture of products and isolation of the required3 -chloropropenenitriles in av ery poor yield might have forced Togo and co-workers [15] to limit their investigationst op ropiophenones.I no ur next attempt to explore the possibility of driving the reactioni nf avour of exclusive formation of 3-chloropropenenitrile 2a,w ef irst isolated 3-chloropropenal 3a,a ni ntermediate in line with the conversion of propiophenones to b-chloro-a-methylcinnamonitriles, andt reatedi tw ith iodine (1 equiv.) and aqueous ammonia in THF which again led to the formation of am ixture of products with 3-chloro-3-phenylpropenenitrile 2a as the predominating product on TLC;t his reinforcedo ur belieft hat it is the second step in the process which is responsible for the side reactions when propiophenone is replacedb y acetophenone.N ext, we envisaged to investigate the effect of substituents andt emperature in order to explore the possibility of driving the reactiont owards exclusive conversion of 3-chloropropenal 3a to 2a (Table 1).…”

“…[15] Unfortunately,t he expected 3-chloropropenitrile was not obtained as as ingle or major isolable product,i nstead ag ummy mass indicating am ixture of productso n TLC was obtained. Repeated purificationo ft he mixture by column chromatographyl ed to the isolation of at iny amount of the predominant product as 3-chloropropenenitrile 2a (Scheme 3).…”

“…Recently,T ogo and co-workers [15] reported as imple one-pot conversion of propiophenones 4 to the corresponding propenenitriles (b-chloro-a-methylcinnamonitriles) 5 (Scheme 2). Surprisingly,t he authors neither included any acetophenone (a simple acetyl derivativeo ther than propiophenone) in the study nor offered any explanation or clue for negating the obvious choice of acetophenones.I tw as interesting as well as intriguing on one hand to ponderu pon the choice of authors not to include acetophenones in the study,o nt he other hand it was tempting to find an answer to this questionb yi nvestigating the fate of acetophenonesu nder the reaction conditions usedb y Togo and co-workers [15] for converting propiophenones to 5.…”

Oppenauer-type synthesis of α, β-acetylenic ketones from tetra(phenylethynyl)tin and aromatic aldehydes

“…One of the most general methods for the synthesis of α-acetylenic ketones is based on the reaction of metal acetylides with aldehydes, followed by oxidation of propargyl alcohols formed [2,5,[8][9][10][11]. Trialkylstannylacetylenes Alk3Sn-C≡C-R are tolerant with respect to many functional groups, therefore they are actively used as alkynylating reagents as well as reagents in crosscoupling reactions [12,13].…”