1569096-83-8Relevant articles and documents
Phosphinic Amide as Directing Group Enabling Palladium(II)-Catalyzed ortho C-H Alkenylation of Anilines without and with Alkylation at the Nitrogen Atom
Jiao, Lin-Yu,Ferreira, André V.,Oestreich, Martin
, p. 367 - 370 (2016)
A phosphinic amide is introduced as a directing group for the ortho C-H alkenylation of anilines. The new donor group distinguishes itself from existing ones by assisting the C-H bond activation of anilides without (NH group) and with alkylation (NMe group) at the amide nitrogen atom. The reactivity is even reversed with the methyl-substituted anilide being more reactive than its unsubstituted counterpart. Electron-donating substituents at the arene ring enhance their reactivity while halogenation is not tolerated. The phosphinic amide also enables the C-7-selective C-H alkenylation of indoline.
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
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.
