The key steps in most organocatalytic cyclizations are the reactions of electrophiles with nucleophiles. Their rates can be calculated by the linear free-energy relationship log k(20 °C) = s(N)(E + N), where electrophiles are characterized by one parameter (E) and nucleophiles are characterized by the solvent-dependent nucleophilicity (N) and sensitivity (s(N)) parameters.Electrophilicity param...

The direct synthesis of nitrile from N2 under mild conditions is great importance and has attracted much interest. Herein, we report a conversion into via nitrile–alkyne cross-metathesis (NACM) process involving N2-derived Mo nitride. Treatment the nitride with alkyne in presence KOTf afforded an alkyne-coordinated nitride, which was then transformed MoV carbyne corresponding upon 1 e? oxidatio...

Substitution effects are probed for novel N-heterocyclic stannylenes (NHSns), including 1,4-di(R)-tetrazole-5-stannylenes (1R), and 1,3-di(R)-tetrazole-5-stannylenes (2R), using B3LYP/6-311++G** level of theory. Nucleophilicity, multiplicity, and stability of 1R and 2R are calculated; with R = H, methyl, ethyl, i-propyl, t-butyl, Ph, OH, methoxy, NO2, CN and CF3. Asymmetric 2H appears more nucl...

Abstract Nitronate anions, formally generated by ?-deprotonating the corresponding nitroalkanes, are highly nucleophilic and versatile intermediates in many carbon–carbon bond-forming reactions. In contrast, silyl nitronates ambiphilic react, at same carbon atom, with both electrophiles nucleophiles. However, while their nucleophilicity has been well exploited catalytic enantioselective reactio...

Abstract New methods for the preparation of a monofluoro-substituted derivative closo -decaborate anion [2-B 10 H 9 F] 2– have been developed. Various synthetic strategies used, where Bu 4 NF, Me KF/18-crown-6, and NH HF 2 act as sources F – anion. A feature proposed is absence fluorinating agent in reaction mixture. In course work, optimal conditions synthesis determined products characterized...

Abstract Organic halide salts in combination with metal or organic compound are the most common and essential catalysts ring‐opening copolymerizations (ROCOP). However, role of was neglected. Here, we have uncovered complex behavior halides ROCOP epoxides aziridine cyclic anhydride. Coordination chain‐ends to cations, electron‐withdrawing effect, leaving ability atoms, chain‐end basicity/nucleo...

A series of pyridinol-blocked isophorone isocyanates, based on pyridinol including 2-hydroxypyridine, 3-hydroxypyridine, and 4-hydroxypyridine, was synthesized and characterized by ¹H-NMR, 13C-NMR, and FTIR spectra. The deblocking temperature of blocked isocyanates was established by thermo-gravimetric analysis (TGA), differential scanning calorimetry (DSC), and the CO₂ evaluation method. The d...

The specific rates of solvolysis of neopentyl chloroformate (1) have been determined in 21 pure and binary solvents at 45.0 °C. In most solvents the values are essentially identical to those for ethyl and n-propyl chloroformates. However, in aqueous-1,1,1,3,3,3-hexafluoro-2-propanol mixtures (HFIP) rich in fluoroalcohol, 1 solvolyses appreciably faster than the other two substrates. Linear free...