Metal‐Mediated CC Bond Formations in Aqueous Media

Dimerization of Terminal Arylalkynes in Aqueous Medium by Ruthenium and Acid Promoted (RAP) Catalysis: Acetate‐ Assisted (sp)C(sp2)C Bond Formation

“…Our investigation developed along the following lines: (i) the choice of the most appropriate reaction conditions for the dimerization of phenylacetylene (1) catalyzed by the complex [{RuClA C H T U N G T R E N N U N G (m-Cl)(h 6 -p-cymene)Cl} 2 ] (I) in aqueous AcOH; (ii) the selection of the most active and selective ruthenium precursor; (iii) the application of the dimerization process to various aromatic terminal alkynes; (iv) the improvement of the reaction efficiency by using additives, in particular acetate salts as cocatalysts.…”

“…[1] In this context, the design and application of transition metal complexes for organic synthesis in water have rendered aqueous organometallic catalysis a rapidly emerging field.…”

Bio- and air-tolerant carbon–carbon bond formations via organometallic ruthenium catalysis

“…A 68:32 ratio of isomeric products 9 and 10 was obtained as a yellowish oil in 58% yield (39.3 mg, 0.307 mmol). Repeated chromatography allowed samples of each isomer to be isolated ( 6,7,12,13-Tetrahydro-5,14-diaza [5]helicinium Trifluoromethanesulfonate (16) Procedure to demonstrate reaction development in transformation 15 → 16. One drop of acetone (0.01 ml) was added directly to the bottom of a RBF containing [Cp*Ru(cod)Cl] 1 (1.7 mg, 4.48 µmol, 25 mole %).…”

“…The resulting solution was stirred at 37°C for 36 h. The reaction mixture was concentrated in vacuo. 1 H NMR analysis indicates formation of 6,7,12,13-tetrahydro-5,14-diaza- [5]helicinium trifluoromethanesulfonate 16 and consumption of the starting material 15 (Fig. 2).…”

Water promoted catalyst-free anti-Markovnikov addition of thiols to styrenes

“…non-toxicity, non-inflammability, high heat capacity, possibility of controlling pH, isolating insoluble solid products by filtration and recycling inorganic catalysts and water itself), allowing organic processes in aqueous medium to be safer, very efficient, and highly selective. 12 The high efficiency and selectivity, and ease of product isolation prompted us to investigate its use for addition of thiols to styrenic substrates.…”