Amine adducts of triallylborane as highly reactive allylborating agents for Cu(I)-catalyzed allylation of chiral sulfinylimines.

The implementation of selective catalytic processes with highly active reagents is an attractive strategy that meets the modern principles of sustainable development of chemistry. In the current study, we for the first time describe the method and general principles of Cu(I)-catalyzed allylation of imines with amine adducts of allylic triorganoboranes. Triallylborane is an extremely reactive compound and cannot be used for the catalytic allylation of imines, whereas its amine adducts are ideal substrates for catalysis. The structure of the amine fragment successfully balances the safety, selectivity and stability of the allylboron reagent, allowing it to demonstrate high activity in catalytic allylation reactions, exceeding many times any known allylboranes. The obtained results are supported by quantitative kinetics data and DFT calculations. The catalytic efficacy of the system was demonstrated on model sulfinylimines (23 examples). High diastereoselectivity up to >99% was achieved, including for the gram-scale synthesis of 2-hydroxyphenyl-derivatives. Taking into account the high reactivity and unsurpassed atom-economy of amine adducts of triallylborane (AAT), they can be considered as prospective allylation reagents with Cu(I) and other appropriate metallocatalysts.

Bilateral metalloheterocyclic systems based on palladacycle and piperidine-2,4-dione pharmacophores.

The design of molecules with effective anticancer properties constructed from both dually active metal complex and organic fragments is a novel trend in medicinal chemistry. This concept suggests the impact of a drug on several biological targets or the synergistic action of both fragments as a single unit. We propose that the combination of a Pd-metallocomplex fragment and an organic unit can be an interesting model for anticancer drug discovery. The first phase in the development of such suggested molecules is the synthesis of bilateral metallosystems containing bioactive 6-substituted piperidin-2-one and a palladated N-phenylpyrazolic fragment. Both fragments were incorporated into one molecule through the fused pyrazole-piperidine-2-one unit followed by pyrazol-directed cyclopalladation of the phenyl-group with Pd(OAc)2. An effect of acceleration of the rate of the palladation by NH-lactam was observed. The synthesized hybrid palladacycles have been characterized and tested for their cytotoxic activity on three cancerous cell lines as PPh3 complexes, revealing structures with potential for further development and structural optimization.

Synthesis of 4-trifluoromethyl-2H-chromenes via the reaction of 2-(trifluoroacetyl)phenols with vinyltriphenylphosphonium chloride.

Substituted on the benzene ring 4-CF3-2H-chromenes have been prepared from substituted 2-(trifluoroacetyl)phenols and vinyltriphenylphosphonium chloride according to the Schweizer protocol in moderate to excellent yields. The influence of the type and the position of aromatic ring substituents on yields of 4-CF3-2H-chromenes have been investigated. It has been shown that 4-CF3-2H-chromenes are convenient precursors to 4-CF3-coumarins.

Dimethylamine adducts of allylic triorganoboranes as effective reagents for Petasis-type homoallylation of primary amines with formaldehyde.

Dimethylamine adducts of triallyl-, triprenyl- and trans-cinnamyl(dipropyl)borane are effective reagents for mild homoallylation of primary amines with aqueous formaldehyde in MeOH without an inert atmosphere. A new concept is proposed for the explanation of the high stability of allylborane-amine adducts in aqueous MeOH.

Adducts of Triallylborane with Ammonia and Aliphatic Amines as Stoichiometric Allylating Agents for Aminoallylation Reaction of Carbonyl Compounds.

Triallylborane-amines adducts are effective stoichiometric allylating agents in the aminoallylation reaction of carbonyl compounds in methanol. Moreover, copper-catalyzed diastereoselective allylation of Ellman's imine was achieved with triallylborane-methylamine adduct.