An Efficient Venus Flytrap for the Reversible Binding of Nitric Oxide

Remarkably efficient reversible binding of nitric oxide (NO) by the stilbenoid derivative 1 is observed (K>3×10⁶ M ⁻¹). This noncovalent interaction is readily controlled by simple oxidation and reduction.     

In Situ Generation of Ruthenium Carbonyl Phosphine Complexes as a Versatile Method for the Development of Enantioselective C−O Bond Arylation

We report here a method for in situ generation of various ruthenium carbonyl phosphine catalysts for arylation via cleavage of inert aromatic carbon–oxygen bonds. The use of catalyst systems consisting of [RuCl₂(CO)(p-cymene)], CsF, styrene, and phosphines enabled facile screening of phosphine ligands. Asymmetric C–O arylation was also achieved for atropo-enantioselective biaryl synthesis using a chiral monodentate phosphine ligand.     

Room-temperature regioselective C-H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates

Mechanistic studies of the ruthenium-catalyzed reaction of aromatic ketones with olefins are presented. Treatment of the original catalyst, RuH(2)(CO)(PPh(3))(3), with trimethylvinylsilane at 90 °C for 1-1.5 h afforded an activated ruthenium catalyst, Ru(o-C(6)H(4)PPh(2))(H)(CO)(PPh(3))(2), as a mixture of four geometric isomers. The activated complex showed high catalytic activity for C-H/olefin coupling, and the reaction of 2'-methylacetophenone with trimethylvinylsilane at room temperature for 48 h gave the corresponding ortho-alkylation product in 99% isolated yield. The activated catalyst was thermally robust and showed excellent catalytic activity under refluxing toluene conditions. (1)H and (31)P NMR studies of the C-H/olefin coupling at room temperature suggested that an ortho-ruthenated complex, P,P'-cis-C,H-cis-Ru(2'-(6'-MeC(6)H(4)C(O)Me))(H)(CO)(PPh(3))(2), participated in the reaction as a key intermediate. Isotope labeling studies using acetophenone-d(5) indicated that the rate-limiting step was the C-C bond formation, not the C-H bond cleavage, and that each step prior to the reductive elimination was reversible. The rate of C-H/olefin coupling was found to exhibit pseudo first-order kinetics and to show first-order dependence on the ruthenium complex concentration.     

Pd-catalyzed copolymerization of methyl acrylate with carbon monoxide: structures, properties and mechanistic aspects toward ligand design

Full details are provided for the alternating copolymerization of acrylic esters with carbon monoxide (CO) catalyzed by palladium species bearing a phosphine-sulfonate bidentate ligand. The copolymer of methyl acrylate (MA) and CO had complete regioregularity with stereocenters that slowly epimerize in the presence of methanol. In the presence of ethylene, terpolymers of MA/ethylene/CO were also prepared. The glass transition temperatures of the co- and terpolymers were higher than that of the ethylene/CO copolymer. Both experimental and theoretical investigations were performed to clarify the superior nature of the palladium phosphine-sulfonate system compared to an unsuccessful conventional palladium diphosphine system: (i) The reversible insertion of CO was directly observed with the isolated alkylpalladium complexes, [{o-((o-MeOC(6)H(4))(2)P)C(6)H(4)SO(3)}PdCH(CO(2)Me)CH(2)COMe], whereas it was not observed with the corresponding complex bearing 1,2-bis(diphenylphosphino)ethane (DPPE). (ii) The transition state of the subsequent MA insertion, the rate-determining step of the catalytic cycle, was lower in energy in the phosphine-sulfonate system than in the DPPE system. This stabilization could be attributed to the less hindered sulfonate moiety as well as the stronger back-donation from palladium to the electron-deficient olefin, which is located trans to the sulfonate.     

Transformation of β-Nitro Alcohols to the Corresponding Nitro Imines with Lithium Hexamethyldisilazide (LHMDS) via Sequential Retro Nitro-Aldol–Nitro-Mannich Reaction

β-Nitro alcohols were converted to the corresponding nitro imines in the presence of lithium hexmethyldisilazide (LHMDS) in one pot. The formal transformation of the hydroxy to imino group proceeded in a sequence of the retro nitro-aldol reaction of β-nitro alcohols and the double nitro-Mannich reaction of the resulting aldimines and nitro alkane dianions.