A facile, practical and eco-friendly protocol for the synthesis of various Z-vinyl thiocyanates under minimal solvent conditions was developed.

Strong Lewis acids of air-stable metallocene bis(perfluorooctanesulfonate)s [M(Cp)(2)][OSO(2)C(8)F(17)](2)⋅nH(2)O⋅THF (M = Zr (2 a⋅3 H(2)O⋅THF), M = Ti (2 b⋅2 H(2)O⋅THF)) were synthesized by the reaction of [M(Cp)(2)]Cl(2) (M = Zr (1 a), M = Ti (1 b)) with nBuLi and C(8)F(17)SO(3)H (2 equiv) or with C(8)F(17)SO(3)Ag (2 equiv). The hydrate numbers (n) of these complexes were variable, changing from 0 to 4 depending on conditions. In contrast to well-known metallocene triflates, these complexes suffered no change in open air for a year. thermogravimetry-differential scanning calorimetry (TG-DSC) analysis showed that 2 a and 2 b were thermally stable at 300 and 180 °C, respectively. These complexes exhibited unusually high solubility in polar organic solvents. Conductivity measurement showed that the complexes (2 a and 2 b) were ionic dissociation in CH(3)CN solution. X-ray analysis result confirmed 2 a⋅3 H(2)O⋅THF was a cationic organometallic Lewis acid. UV/Vis spectra showed a significant red shift due to the strong complex formation between 10-methylacridone and 2 a. Fluorescence spectra showed that the Lewis acidity of 2 a fell between those of Sc(3+) (λ(em)=474 nm) and Fe(3+) (λ(em)=478 nm). ESR spectra showed the Lewis acidity of 2 a (0.91 eV) was at the same level as that of Sc(3+) (1.00 eV) and Y(3+) (0.85 eV), while the Lewis acidity of 2 b (1.06 eV) was larger than that of Sc(3+) (1.00 eV) and Y(3+) (0.85 eV). They showed high catalytic ability in carbonyl-compound transformation reactions, such as the Mannich reaction, the Mukaiyama aldol reaction, allylation of aldehydes, the Friedel-Crafts acylation of alkyl aromatic ethers, and cyclotrimerization of ketones. Moreover, the complexes possessed good reusability. On account of their excellent catalytic efficiency, stability, and reusability, the complexes will find broad catalytic applications in organic synthesis.

An economic, safe, practical, and environmentally benign protocol for the oxidation of aldehydes to carboxylic acids and acid anhydrides with ambient air as the sole oxidant was developed. This oxidation is operationally simple and external catalyst-, initiator-, and base-free, with outstanding functional group tolerance (moisture-, acid-, base-, and oxidant-sensitive groups). It also provides a practical protocol for large scale synthesis (>100 g), late-stage modification of polyfunctional compounds, and one-pot sequential transformation starting from aldehydes.

Nickel-catalyzed thiolation of the inactivated methyl C(sp(3))-H bonds of aliphatic amides with disulfide is described. It is a novel strategy for the synthesis of thioethers with the ultimate goal of generating thioether carboxylic acids with various functional groups.