Multiple arylation of alkyl aryl ketones and α,β-unsaturated carbonyl compounds via palladium catalysis

Ruthenium(II) Acetate Catalyst for Direct Functionalisation of sp2‐CH Bonds with Aryl Chlorides and Access to Tris‐ Heterocyclic Molecules

“…2-Chloro-and 2-bromothiophenes react with 2-pyridylbenzene 3 in the presence of [RuCl 2 A C H T U N G T R E N N U N G (pcymene)] 2 1 and in situ made RuA C H T U N G T R E N N U N G (OAc) 2 A C H T U N G T R E N N U N G (p-cymene) 2 to afford tripodal molecules containing two thiophenyl groups separated by a 2-pyridyl group linked to a benzene ring: 13a, 13d and 13c [Eqs. (3) and (4), Table 3). The reaction conditions are much milder than those required for the reactions with halopyridynes (Table 2) as the dithiophenylated products 13a and 13b can be quantitatively obtained after 12 h at 120 8C.…”

“…[2] Direct arylations of functional arenes or alkenes have recently been performed using palladium(0) catalyst precursors. [3][4][5] Direct arylations of phenols [6] or heterocycles [7] can also be performed with rhodium [7] and iridium catalysts. [8] Recently, ruthenium(II) catalysts based on a RuCl 2 (hydrocarbon) source associated with various ligands have emerged as possible catalysts for C À H bond arylation and allylation.…”

“…Comparison of experiments with K 2 CO 3 only (entries 3,7,9) shows that the diarylation with aryl chlorides is only slightly favoured by a para electron-withdrawing group R (R = MeCO > H > MeO).…”

Nickel‐Catalyzed Formation of a Carbon–Nitrogen Bond at the β Position of Saturated Ketones

“…[2] However, bond formation on the b-carbon atom of saturated ketones still remains unexplored. [3][4][5][6][7][8] Herein, we describe a new catalytic formation of a carbonnitrogen bond at the b position of alkyl ketones in the presence of a nickel complex.…”

Catalytic Methods for CH Bond Functionalization: Application in Organic Synthesis

“…The phosphorus atom coordinates to the rhodium atom, then electrophilic substitution with the rhodium(III) species occurs at the ortho position. The palladium-catalyzed arylations of aromatic carbonyl compounds such as ketones, [104] amides, [105] and aldehydes [106] with aryl halides lead to the multiple arylation products (Scheme 7). A plausible pathway is as follows: an anion exchange between the amido anion (or enolate) and triflate (or halide) ion in the Ar-Pd-X species leads to the (aryl)(alkoxy)palladium intermediate 11; electrophilic palladation on the aromatic ring gives the Ar-Pd-Ar× intermediate 12; the reductive elimination affords the diaryl compounds.…”