Cyclization of C-phosphorylated (PIII) arylformamidines to 3H-1,3-benzazaphospholes

Marchenko, A. P.; Koidan, Heorgii; Hurieva, Anastasiya; Merkulov, A. E.; Пинчук, А. M.; Yurchenko, A. A.; Rozhenko, Alexander; Jones, Peter G.; Thönnessen, Holger; Kostyuk, Alexander

doi:10.1016/j.tet.2011.08.007

Cited by 45 publications

(14 citation statements)

References 23 publications

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“…NMR spectra of 7 and 8 are consistent with the literature data [18]. It was found that 2a,b readily reacted with dimethylamine and selenium (Scheme 4).…”

Section: Resultssupporting

confidence: 86%

“…The reaction mixture was allowed to warm to 15°C and after 1 h, 31 P NMR of the reaction mixture confirmed the formation of benzaazphospholes 9 (δ p 61 for both 9a and 9b) [18]. The temperature of the reaction mixture was raised to 20°C for 5 min, kept for 1 h, and then cooled to -20°C, and a solution of Me 2 NH (0.01 mol) in CH 2 Cl 2 (5 mL) was added.…”

Section: Synthesis Of 10mentioning

confidence: 99%

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Zwitterionic Phosphoranides as Intermediates in the Reaction of Phosphorus Tribromide with N,N‐Dimethyl‐N′‐arylformamidines

Marchenko

Koidan

Hurieva

et al. 2015

Heteroatom Chemistry

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Cyclic zwitterionic phosphoranides 2a,b were found to be intermediate products in the reaction of N,N‐dimethyl‐N′‐(aryl)formamidines with PBr3. The structure of phosphoranide 2a was determined by means of the X‐ray and quantum chemistry investigations. Mechanism of its formation was proposed based on Density functional theory (DFT) calculations. Reactions of 2 with amines and selenium yielded either C‐phosphorylated formamidines or benzazaphospholes. The first example of intramolecular heterocyclization of a pentavalent phosphorus derivative 15b into 3Н‐1,3‐benzazaphosphole has been demonstrated.

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“…NMR spectra of 7 and 8 are consistent with the literature data [18]. It was found that 2a,b readily reacted with dimethylamine and selenium (Scheme 4).…”

Section: Resultssupporting

confidence: 86%

Section: Synthesis Of 10mentioning

confidence: 99%

Zwitterionic Phosphoranides as Intermediates in the Reaction of Phosphorus Tribromide with N,N‐Dimethyl‐N′‐arylformamidines

Marchenko

Koidan

Hurieva

et al. 2015

Heteroatom Chemistry

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“…As in the previous case, the 1 H NMR spectrum proved difficult to interpret, and thus the structure was solved by single‐crystal X‐ray analysis (Figure ). The data for compound 7 is consistent with a benzazaphosphole derivative, the synthesis of which can be rationalized by the formation of intermediate chlorophosphane 7′ , which cyclizes to benzazaphosphole 7 as do similar compounds previously described …”

Section: Resultssupporting

confidence: 80%

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

et al. 2016

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A method for the synthesis of new C‐silyl‐N,N‐dialkyl‐N′‐arylformamidines was developed. These derivatives were formed by the deprotonation of N‐(trimethylsilyl)formamidinium salts to give the corresponding N‐trimethylsilyl carbenes followed by a 1,2‐migration of the silyl group. The reactions of C‐silylformamidines with phosphorus(III) chlorides were then studied. The reactions between chlorodiphenylphosphane and the C‐silylformamidines readily afforded C‐phosphanylformamidines in high yields. The reactions of dichlorophosphanes and C‐silylformamidines yielded previously unknown phosphanes that feature two formamidine substituents. In the reaction with phosphorus trichloride, the sterically least encumbered formamidine gave a stable two‐coordinate compound through the formation of an intermediate tris(phosphane). The reactions of the sterically more encumbered formamidines led to the substitution of only two chlorine atoms to give a chlorophosphane or benzazaphosphole. The structures of key compounds were proven by X‐ray crystal structure analyses.

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“…In our previous work, we showed that the cyclization of C ‐phosphorylated N,N ‐dimethyl‐N′‐arylformamidines critically depends on the position and electron‐donating capability of substituents at the aryl ring (Scheme ). The cyclization proceeds with the elimination of dimethylamine and its mechanism was described in detail [6b]. Electron‐donating substituents at the meta position promoted cyclization the best.…”

Section: Resultsmentioning

confidence: 99%

“…The rate of the cyclization has been shown to depend on the benzene ring substituent electron‐donating efficiency. At the same time, the method tolerates various substituents . In this contribution, we describe the extension of the method to 1,3‐diaminobenzene and 1,3,5‐triaminobenzene to prepare polycyclic 3 H ‐1,3‐benzazaphospholes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Bis‐ and Tris(3‐H‐1,3‐azaphospholo)benzenes

Marchenko

Koidan

Huryeva

et al. 2013

Heteroatom Chemistry

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The previously developed intramolecular cyclocondensation of C‐phosphanyl(N‐aryl)formamidines into 3‐H‐1,3‐benzazaphospholes has been successfully extended to 1,3‐diaminobenzene and 1,3,5‐triaminobenzene. Its condensation presents the way to tricyclic and tetracyclic azaphospholes. Their structures were confirmed by spectroscopic methods and key tricyclic and tetracyclic compounds were further characterized by single crystal X‐ray diffraction.

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Cyclization of C-phosphorylated (PIII) arylformamidines to 3H-1,3-benzazaphospholes

Cited by 45 publications

References 23 publications

Zwitterionic Phosphoranides as Intermediates in the Reaction of Phosphorus Tribromide with N,N‐Dimethyl‐N′‐arylformamidines

Zwitterionic Phosphoranides as Intermediates in the Reaction of Phosphorus Tribromide with N,N‐Dimethyl‐N′‐arylformamidines

C‐Silyl‐N,N‐dialkyl‐N′‐arylformamidines: Synthesis and Reactions with Phosphorus(III) Chlorides

Synthesis of Bis‐ and Tris(3‐H‐1,3‐azaphospholo)benzenes

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