56898-59-0Relevant articles and documents
Transformation Routes of PV- and PIII-N-Substituted Acyclic Diaminocarbenes
Marchenko, Anatoliy,Koidan, Georgyi,Hurieva, Anastasiya,Vlasenko, Yurii,Rozhenko, Alexander B.,Sotiropoulos, Jean-Marc,Kostyuk, Aleksandr
, p. 1621 - 1632 (2019)
Herein we report on the synthesis of a set of transient N-(PIII)-phosphanyl and N-(PV)-phosphoroselenoyl acyclic diaminocarbenes by deprotonation of the corresponding formamidinium salts. It is shown that N-(PV)-substituted acyclic diaminocarbenes undergo 1,2-phosphorus shift. Transformations of N-(PIII)-substituted acyclic diaminocarbenes result in tetrahydroquinazolines as final products. The proposed mechanism includes the isomerization of the carbenes into transient azomethine ylides followed by their cyclization via electrophilic aromatic substitution. Introduction of the electron-donating dimetylamino group into the phenyl substituent markedly enhances the rate of the reaction and the yield of the final product. In the case of the morpholine derivative, the corresponding azomethine ylide undergoes opening the morpholine ring giving vinyloxazolidin-2-amine. The results are corroborated by DFT calculations.
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
supporting information, p. 367 - 370 (2016/05/19)
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.
Hydrophosphination of vinyl-boranes with phosphinoamines
Jiang, Chunfang,Stephan, Douglas W.
, p. 3318 - 3325 (2013/03/29)
Phosphinoamine ligands PhN(H)PR2 (R = iPr 1, tBu 2) react with R1CHCR2B(C6F5)2 (R 1 = Ph, p-FC6H4, nPr, Et, R2 = H, Ph, Et, C6F5
SOME NEW PHOSPHINIC AMIDES R2P(O)NHR'
Brueck, A.,Kuchen, W.,Peters, W.
, p. 129 - 134 (2007/10/03)
P,P-Diorganylphosphinic amides R2P(O)NHR' (R = tBu, iPr, Ph; R' = Et, Pr, Cy, iPr, tBu, Ph, etc.) have been prepared by reaction of R2PCl with the corresponding lithiated amine followed by oxidation with H2O2.Th
