Abstract A series of fluoropyridines featuring a N,N,N’ ‐trimethyl, N’ ‐trimethylsilylaminal group were subjected to methanolysis. The methanolysis carried out at room temperature yielded mixture products. aminal was transformed into methylimine and ensuing dimethylamine substituted (or not) fluorine atom. relative content pyridine methylimines with dimethylamino without it determined for all fluoropyridines. Additionally, these compounds hydrolyzed aldehydes. This work presents novel...

N-Phosphanyl-N-heterocyclic carbenes (NHCPs) featuring a saturated imidazolin-2-ylidene or tetrahydropyrimid-2-ylidene ring have been synthesized and characterized. The free exhibit good stability can be stored in the solid state for months at ambient temperature without decomposition. Contrary to imidazoline-based NHCPs, which decompose by opening, N-phosphanyltetrahydropyrimid-2-ylidenes isomerize 2-phosphanyl tetrahydropyrimidines upon heating. are capable of acting as chelating ligands...

Complexes of palladium(II) with newly disclosed, N-phosphanyl acyclic diaminocarbene ligands are synthesized for the first time and structurally characterized. The coordinate in a chelating fashion, yielding remarkably stable complexes which can be stored without special precautions solid state. Related an isomerized ligand, formed upon 1,2-migration phosphanyl group from nitrogen to adjacent carbon atom, have also been isolated some instances efficiently act as precatalysts Suzuki coupling...

A novel method for synthesis of medium sized ring azasultams was proposed.

Abstract The deprotonation of N ‐di‐ tert ‐butylphosphanyl‐ ‐aryl‐ N′ ‐diisopropylformamidinium salts led to a new type stable acyclic ‐phosphanyl‐diaminocarbene (PADC). Carbenes 8a – 8d were separated as single compounds. molecular structure 8c was determined by X‐ray diffraction analysis. PADC 8 possess an optimal substitution pattern at the nitrogen atoms, and N–C carbene –N bond angle is 120.7°. Structural changes near carbenic carbon atom, such phenyl with mesityl, phosphanyl...

Enamine tautomerism is often the main cause of regio­selectivity problems in chemistry enamines derived from ­ketones. Linear push-pull tertiary featuring a methyl ­(methylene) group at α-position do not experience such tau­to­merism; nevertheless, number reactions proceed with participation (methylene) group. It was our objective to analyze all known this type and show their high synthetic potential.

A small library of dinuclear gold(I) complexes with the title ligands has been prepared, encompassing neutral, mono- and dicationic complexes. The luminescence properties in solid state have evaluated, it turns out that neutral monocationic not presenting a rigid metallamacrocyclic structure can exhibit rather strong emissions extend towards red region visible spectrum. vitro anticancer activity also preliminarly evaluated; cytotoxicity seems to correlate complex lipophilicity, whereas...

Using DFT and ab initio calculations, we demonstrate that noncyclic formamidines can undergo thermal rearrangement into their isomeric aminocarbenes under rather mild conditions. We synthesized the silylformamidine, for which lowest activation energy in this process was predicted. Experimental studies proved it to serve as a very reactive nucleophilic carbene. The reactions with acetylenes, benzenes, trifluoromethane proceeded via insertion sp, sp2, sp3 CH bonds. carbene also reacted...

Abstract A convenient method for the synthesis of 10‐ and 11‐membered azalactams via reductive cleavage bicyclic systems featuring an amidine fragment was studied. It found that ring‐expansion reaction dihydropyrimidones depends on ring size saturated fragment, substituents in pyrimidone core conditions. new efficient medium by quaternary salts annulated proposed as well. The obtained with a secondary amine function were used heteroaromatic systems.

Silylformamidine 1 exists in equilibrium with its carbenic form 1′ due to an easy migration of the silyl group. The reaction variously substituted fluorobenzenes proceeds as insertion nucleophilic carbene into most acidic C–H bond upon mixing reagents and does not require any catalyst. According DFT calculations, classical interpretation proceeding via a three-membered transition state structure requires high activation energy. Instead, low barriers are predicted for transfer proton aromatic...

A novel two-step method for formylation of fluoropyridines with silylformamidine Me3 SiC(=NMe)NMe2 (1) under catalyst-free conditions was developed. series all possible 18 featuring one to four fluorine atoms were subjected the reaction 1 existing in equilibrium its carbenic form Me2 NC(:)N(Me)SiMe3 (1'). Among them, 12 shown react via C-H insertion. The proceeded either at β- or γ-positions affording corresponding aminals. more pyridines, easier proceeded. We also hypothesized that...

Abstract We studied the reaction of N ‐alkyl(aryl)pyrazoles with silylformamidine 1 that exists in an equilibrium its carbene form via migration trimethylsilyl group from carbon to nitrogen atom. The insertion proceeded at C−H 5 th position. featuring substituents such as Br, CN and NO 2 reacted readily affording corresponding aminals. This approach allowed us synthesize pyrazole dialdehyde phosphine a vicinal aldehyde group. does not require any catalyst. position was unambiguously...

Cancer still remains a major public health concern around the world and search for new potential antitumor molecules is essential fighting disease. This study evaluated anticancer immunomodulatory of newly synthetized ellipticine derivate: sodium bromo-5,11-dimethyl-6H-pyrido[4,3-b]carbazole-7-sulfonate (Br-Ell-SO3Na). It was prepared by chlorosulfonation 9-bromoellipticine. The ellipticine-7-sulfonic acid itself not soluble, but its saponification with hydroxide afforded water-soluble salt....

Abstract A convenient method to easily prepare parent λ 3 ‐phosphinine from accessible 5 ‐precursors was developed. series of ‐phosphinines bearing heteroatom substituents OMe, SMe, and/or NMe 2 at the phosphorus atom were prepared by electrocyclization phosphahexatrienes generated in situ. Reaction conditions for synthesis optimized. The molecular structure 1,1‐dimethoxy‐λ determined an X‐ray diffraction analysis. reducing agents tested order ‐phosphinine. 1,1‐Dimethoxy‐λ reduced LiAlH 4 ....

A new N ‐diadamantylphosphanyldiaminocarbene 5 is prepared, isolated, and characterized. The carbene appears to be much more stable than previously reported di‐ tert ‐butyl congeners. molecular structure of the determined by X‐ray diffraction analysis. (diisopropylamino)(diadamantylphosphanyl)carbene 8 also prepared in situ, but not since this case, adamantyl groups do render stable, with respect known carbenes substitution. Carbene reacts situ phenylazide give iminophosphane 9 , which...

The catalytic potential of palladium(II) complexes with chelating N-phosphanyl-N-heterocyclic carbenes featuring a saturated imidazolin-2-ylidene or tetrahydropyrimid-2-ylidene ring has been investigated in intermolecular alkyne hydroamination reactions. were found to be among the most active Pd-based catalysts for these processes and enable use low reaction temperatures (40 °C) solventless conditions. Pd require activation by 2 equiv silver salt remove chlorido ligands from metal...

Abstract The reactions of (di‐ tert ‐butylphosphanyl)amines and P , ‐di‐ ‐butylphosphinoselenoic amides with Alder's dimer were studied. For di‐ ‐butylphosphanylamines, the reaction proceeds by primary electrophilic attack at phosphorus atom to afford a dicationic salt 3 . deprotonation led N ‐phosphanylformamidine 5 (“phosfam”). Alkyl(di‐ reacted in 2:1 molar ratio give ‐phosphanylformamidinium salts; second equivalent (alkylamino)phosphane acts as base. (Arylamino)phosphanes...