The cationic complex [(pymox-Me(2))RuCl(2)](+)BF(4)(-) was found to be a highly effective catalyst for the C-H bond oxidation reaction of arylalkanes in water. For example, the treatment of ethylbenzene (1.0 mmol) with t-BuOOH (3.0 mmol) and 1.0 mol % of the Ru catalyst in water (3 mL) cleanly produced PhCOCH(3) at room temperature. Both a large kinetic isotope effect (k(H)/k(D) = 14) and a rel...

Intramolecular nucleophilic aromatic substitution (Truce–Smiles rearrangement) of the anions 2-benzyl benzanilides leads to triarylmethanes in an operationally simple manner. The reaction succeeds even without electronic activation ring that plays role electrophile SNAr reaction, being accelerated instead by preferred conformation imposed tertiary amide tether. substituent product may be remove...

The ability of the present semiempirical quantum mechanics methods are surveyed for reproducing the transannular interaction in the bifunctional N-phenyl-5-azocanones. The AM1 method is the best with the order of reliability being Am1, PM3, MNDO and MINDO/3. AM1 calculations were then carried out for quantification of transannular interaction. The n(o) ionization potential has be...

γ,δ-Unsaturated amino acids are the backbone of various natural products and pharmaceuticals, while quaternary α-amino also powerful enzyme inhibitors, both very important compounds in bioorganic chemistry. A highly efficient synthesis γ,δ-unsaturated esters utilizing tandem umpolung/Claisen rearrangement for α-iminoallyl was developed. This method has a wide range substrates taking account Ham...

Dependence of the hydrolysis rate a series N-methoxy-2-phenyl-1,3-oxazinanes on Hammett substituent constant phenyl ring was determined, yielding reaction ρ=−1.40±0.05. Based this information, 4-(benzoyloxy)benzaldehyde selected as protecting group for new (2R,3S)-4-(methoxyamino)butane-1,2,3-triol phosphoramidite building block. The yield preparation block well its coupling in automated oligon...