98688-18-7Relevant academic research and scientific papers
CNN pincer ruthenium complexes for efficient transfer hydrogenation of biomass-derived carbonyl compounds
Figliolia, Rosario,Cavigli, Paolo,Comuzzi, Clara,Del Zotto, Alessandro,Lovison, Denise,Strazzolini, Paolo,Susmel, Sabina,Zuccaccia, Daniele,Ballico, Maurizio,Baratta, Walter
supporting information, p. 453 - 465 (2020/01/21)
The ligand HCNNOMe (6-(4-methoxyphenyl)-2-aminomethylpyridine) is easily prepared from the commercially available 6-(4-methoxyphenyl)pyridine-2-carbaldehyde by the reaction of hydroxylamine and hydrogenation (H2, 1 atm) with Pd/C. The pincer complexes cis-[RuCl(CNNOMe)(PPh3)2] (1) and [RuCl(CNNOMe)(PP)] (PP = dppb, 2; and dppf, 3) are synthesized from [RuCl2(PPh3)3], HCNNOMe and PP (for 2 and 3) in 2-propanol with NEt3 at reflux and are isolated in 85-93% yield. Carbonylation of 1 (CO, 1 atm) gives [RuCl(CNNOMe)(CO)(PPh3)] (4) (79% yield) which cleanly reacts with Na[BArf4] and PCy3, affording the cationic trans-[Ru(CNNOMe)(CO)(PCy3)(PPh3)][BArf4] (5) (92% yield). These robust pincer complexes display remarkably high catalytic activity in the transfer hydrogenation (TH) of lignocellulosic biomass carbonyl compounds, using 2-propanol at reflux in a basic medium (NaOiPr or K2CO3). Thus, furfural, 5-(hydroxymethyl)furfural and Cyrene are reduced to the corresponding alcohols with 2 and 3, at S/C in the range of 10 000-100 000, within minutes or hours (TOF up to 1 500 000 h-1). The monocarbonyl complex 5 was found to be extremely active in the TH of cinnamaldehyde, vanillin derivatives and ethyl levulinate at S/C in the range of 10 000-50 000. Vanillyl alcohol is also obtained by the TH of vanillin with 5 (S/C = 500) in 2-propanol in the presence of K2CO3.
Two-step synthesis of D3 and C3h cryptophanes
Canceill, Josette,Collet, Andre
, p. 582 - 584 (2007/10/02)
Dihalides X-(Z)-X, [Z = (CH2)n; n = 1-7 or CH 2CH=CHCH2] react with the phenol group of vanillyl alcohol to give the dialkylated derivatives HOCH2-Ar-O-(Z)-O-Ar-CH 2OH (2), which in turn, in the presence of formic acid, afford the corresponding D3 cryptophanes (3), with, in some cases, minor amounts of the C3h isomers (4).
Analytical Optical Resolution of Bromochlorofluoromethane by Enantioselective Inclusion into a Tailor-Made "Cryptophane" and Determination of Its Maximum Rotation
Canceill, Josette,Lacombe, Liliane,Collet, Andre
, p. 6993 - 6996 (2007/10/02)
Analytical optical resolution of bromochlorofluoromethane (1) has been achieved by 1H NMR spectroscopy by inclusion of the haloform within the cavity of a chiral host molecule (5) (cryptophane-C) designed to fit substrates of this size.The diastereometric
