1569097-08-0Relevant academic research and scientific papers
Palladium(ii) complexes with chelating N-phosphanyl acyclic diaminocarbenes: Synthesis, characterization and catalytic performance in Suzuki couplings
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Vlasenko, Yurii,Kostyuk, Aleksandr,Biffis, Andrea
, p. 1967 - 1975 (2016/02/05)
Complexes of palladium(ii) with newly disclosed, N-phosphanyl acyclic diaminocarbene ligands are synthesized for the first time and structurally characterized. The ligands coordinate palladium(ii) in a chelating fashion, yielding remarkably stable complexes which can be stored without special precautions in the solid state. Related palladium(ii) complexes with an isomerized chelating ligand, formed upon 1,2-migration of the phosphanyl group from the nitrogen to the adjacent carbon atom, have also been isolated in some instances and structurally characterized. The complexes efficiently act as precatalysts for Suzuki coupling reactions of aryl chlorides, where their productivity compares favourably with that of related palladium complexes with acyclic diaminocarbene ligands. In addition, the complexes show a distinct tendency to form as the byproduct the reductive homocoupling product of aryl chloride. This observation, together with ad hoc performed control tests, suggests that Pd colloids are involved in the formation of catalytically competent species.
Stable N-phosphanyl acyclic diaminocarbenes
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Kurpiieva, Olena,Vlasenko, Yurii,Rozhenko, Alexander B.,Kostyuk, Aleksandr
, p. 3259 - 3270 (2015/04/27)
The deprotonation of N-di-tert-butylphosphanyl-N-aryl-N′-diisopropylformamidinium salts led to a new type of stable acyclic N-phosphanyl-diaminocarbene (PADC). Carbenes 8a-8d were separated as single compounds. The molecular structure of 8c was determined by X-ray diffraction analysis. The PADC 8 possess an optimal substitution pattern at the nitrogen atoms, and the N-Ccarbene-N bond angle is 120.7°. Structural changes near the carbenic carbon atom, such as substitution of phenyl with mesityl, phosphanyl with selenophosphoryl, or the diisopropylamino group with 2,2,6,6-tetramethylpiperidino, rendered them unstable. The PADCs underwent N,C-phosphorus shifts to afford new C-phosphanylformamidines. The deprotonation of PIII N-substituted formamidinium salts afforded a new type of stable acyclic N-phosphanyl-diaminocarbene. The carbenes possess an optimal substitution pattern, deviations from which make them unstable. They transform into C-phosphanylformamidines by a N,C-phosphorus shift, which was studied by quantum chemistry calculations.
A convenient approach to N-(di-tert-butylphosphanyl)- and N-(di-tert-butylphosphoroselenoyl)formamidinium salts: Carbene precursors
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Savateev, Aleksandr,Rozhenko, Alexander B.,Sotiropoulos, Jean-Marc,Shishkina, Svitlana V.,Shishkin, Oleg V.,Kostyuk, Aleksandr
, p. 1192 - 1203 (2015/04/27)
The reactions of (di-tert-butylphosphanyl)amines and P,P-di-tert-butylphosphinoselenoic amides with Alder's dimer were studied. For di-tert-butylphosphanylamines, the reaction proceeds by primary electrophilic attack of Alder's dimer at the phosphorus atom to afford a dicationic salt 3. The deprotonation of 3 led to N-phosphanylformamidine 5 ( phosfam ). Alkyl(di-tert-butylphosphanyl)amines reacted with Alder's dimer in a 2:1 molar ratio to give N-phosphanylformamidinium salts; the second equivalent of (alkylamino)phosphane acts as a base. (Arylamino)phosphanes reacted with Alder's dimer to give benzazaphospholium derivatives. To direct the electrophilic attack of Alder's dimer at the nitrogen atom, phosphinoselenoic amides were used. They reacted with Alder's dimer at the selenium atom followed by a selenium-phosphorus shift to give N-(di-tert-butylphosphoroselenoyl)formamidinium salts. The phosphinoselenoic amides with bulky substituents (adamantyl, tBu) underwent cleavage of the N-alkyl bond to afford phosfams. Various key intermediates such as 3 and 22b were isolated and characterized. A convenient method for the synthesis of carbene precursor PIII and PV N-substituted formamidinium salts was developed. Carbene precursor PIII and PV N-substituted formamidinium salts are obtained by the reaction of (di-tert-butylphosphanyl)amines and P,P-di-tert-butylphosphinoselenoic amides with Alder's dimer. The primary electrophilic attack of Alder's dimer proceeds at the phosphorus atom of the phosphanylamines or at the selenium atom of the phosphinoselenoic amides.
Stable N-phosphanyl acyclic diaminocarbenes
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Kurpiieva, Olena,Vlasenko, Yurii,Rozhenko, Alexander B.,Kostyuk, Aleksandr
, p. 3259 - 3270 (2014/07/22)
The deprotonation of N-di-tert-butylphosphanyl-N-aryl-N′- diisopropylformamidinium salts led to a new type of stable acyclic N-phosphanyl-diaminocarbene (PADC). Carbenes 8a-8d were separated as single compounds. The molecular structure of 8c was determined by X-ray diffraction analysis. The PADC 8 possess an optimal substitution pattern at the nitrogen atoms, and the N-Ccarbene-N bond angle is 120.7°. Structural changes near the carbenic carbon atom, such as substitution of phenyl with mesityl, phosphanyl with selenophosphoryl, or the diisopropylamino group with 2,2,6,6-tetramethylpiperidino, rendered them unstable. The PADCs underwent N,C-phosphorus shifts to afford new C-phosphanylformamidines. The deprotonation of PIII N-substituted formamidinium salts afforded a new type of stable acyclic N-phosphanyl-diaminocarbene. The carbenes possess an optimal substitution pattern, deviations from which make them unstable. They transform into C-phosphanylformamidines by a N,C-phosphorus shift, which was studied by quantum chemistry calculations. Copyright
A convenient approach to N-(Di-tert-butylphosphanyl)- and N-(Di-tert-butylphosphoroselenoyl)formamidinium Salts: Carbene precursors
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Savateev, Aleksandr,Rozhenko, Alexander B.,Sotiropoulos, Jean-Marc,Shishkina, Svitlana V.,Shishkin, Oleg V.,Kostyuk, Aleksandr
, p. 1192 - 1203 (2014/03/21)
The reactions of (di-tert-butylphosphanyl)amines and P,P-di-tert- butylphosphinoselenoic amides with Alder's dimer were studied. For di-tert-butylphosphanylamines, the reaction proceeds by primary electrophilic attack of Alder's dimer at the phosphorus atom to afford a dicationic salt 3. The deprotonation of 3 led to N-phosphanylformamidine 5 ( phosfam ). Alkyl(di-tert-butylphosphanyl)amines reacted with Alder's dimer in a 2:1 molar ratio to give N-phosphanylformamidinium salts; the second equivalent of (alkylamino)phosphane acts as a base. (Arylamino)phosphanes reacted with Alder's dimer to give benzazaphospholium derivatives. To direct the electrophilic attack of Alder's dimer at the nitrogen atom, phosphinoselenoic amides were used. They reacted with Alder's dimer at the selenium atom followed by a selenium-phosphorus shift to give N-(di-tert-butylphosphoroselenoyl) formamidinium salts. The phosphinoselenoic amides with bulky substituents (adamantyl, tBu) underwent cleavage of the N-alkyl bond to afford phosfams. Various key intermediates such as 3 and 22b were isolated and characterized. A convenient method for the synthesis of carbene precursor PIII and PV N-substituted formamidinium salts was developed. Carbene precursor PIII and PV N-substituted formamidinium salts are obtained by the reaction of (di-tert-butylphosphanyl)amines and P,P-di-tert-butylphosphinoselenoic amides with Alder's dimer. The primary electrophilic attack of Alder's dimer proceeds at the phosphorus atom of the phosphanylamines or at the selenium atom of the phosphinoselenoic amides. Copyright
