1,3,6‐Azadiphosphacycloheptanes: A novel type of heterocyclic diphosphines

Карасик, А. А.; Balueva, A. S.; Moussina, Elvira I.; Naumov, Roman N.; Dobrynin, A. B.; Krivolapov, Dmitry B.; Литвинов, И. А.; Sinyashin, Оleg G.

doi:10.1002/hc.20397

Cited by 37 publications

(31 citation statements)

References 30 publications

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“…After one half of hour two additional sets of signals appeared in the NMR spectra (e.g. 45 The signals of two new components in 1 H and 31 P spectra are situated in the same regions and have the same intensity and multiplicity relationships as in described 7-membered heterocycles 8 suggesting that they have chemically close 50 structure. Intensities of new sets of signals increased with time while the signals ascribed to 14-membered macrocycle diminished.…”

Section: Resultsmentioning

confidence: 98%

Synthesis and unique reversible splitting of 14-membered cyclic aminomethylphosphines on to 7-membered heterocycles

et al. 2015

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A novel type of 14-membered cyclic polyphosphine, namely 1,8-diaza-3,6,10,13-tetraphosphacyclotetradecanes 2a–4ahas been synthesized by the condensation of 1,2-bis(phenylphosphino)ethane, formaldehyde and alkylamines (isopropylamine, ethylamine and cyclohexylamine) as a RRRR/SSSS-stereoisomer. The structure of macrocycle 2a was investigated by NMR-spectroscopy and X-ray crystal structure analysis. The unique reversible processes of macrocycles 2a–4a splitting onto the corresponding rac- (2b–4b) and meso- (2c–4c) stereoisomers of 1-aza-3,6-diphosphacycloheptanes were discovered.

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Section: Resultsmentioning

confidence: 98%

Synthesis and unique reversible splitting of 14-membered cyclic aminomethylphosphines on to 7-membered heterocycles

et al. 2015

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“…The X-ray structure analysis unambiguously established the configurations of 3 RRS in the solid state ( Figure 4, Table 1), as well as the typical twist-chair conformation of the seven-membered ring. [23] The nitrogen atom is in a pyramidal environment (the sum of the bond angles is 337.81°), and the exocyclic substituent on the nitrogen atom is in an axial position. [23] The nitrogen atom is in a pyramidal environment (the sum of the bond angles is 337.81°), and the exocyclic substituent on the nitrogen atom is in an axial position.…”

Section: Synthesesmentioning

confidence: 94%

“…The seven-membered rings in 3 RSS and 4 RSR exhibit unusual chair conformations with almost planar P-C-C-P fragments [the torsion angles P(3)-C(4)-C(5)-P(6) in 3 RSS and 4 RSR are -2.1 and 8.0°, respectively (Table 1)] with the P-C bonds in eclipsed positions. [23] The nitrogen To the best of our knowledge, up to now stable chair conformations have only been described for cycloheptanes with rigid benzo groups or unsaturated ethene-1,2-diyl fragments linking the phosphorus atoms. The P(3)···P(6) distances are short (3.120 and 3.118 Å for 3 RSS and 4 RSR , respectively) in comparison with P···P distances within known rac isomers of 1-aza-3,6-diphosphacycloheptanes (3.599-3.985 Å).…”

Section: Synthesesmentioning

confidence: 99%

“…[23] The signals of the protons of the P-CH 2 -N fragments were observed as complex multiplets and a broad doublets in the 1 H NMR spectra of 6-8. The 31 P NMR spectra of 6 and 7 showed two peaks (27.8 and 27.9 ppm, 26.5 and 26.6 ppm, respectively) with coupling constants 1 J PtP in the range of 3219-3230 Hz, which is typical for cis-chelate P,P complexes of cyclic aminomethylphosphanes of PtCl 2 .…”

Section: Platinum(ii) Complexes Of 1-aza-36diphosphacycloheptanesmentioning

confidence: 99%

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Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

et al. 2012

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Cyclic seven-membered bisphosphanes, namely 1-aza-3,6diphosphacycloheptanes 3-5 (3: 3,6-diphenyl-1-(1-phenylethyl)-1-aza-3,6-diphosphacycloheptane; 4: 1-[(1R)-1-(4Јmethoxyphenyl)ethyl]-3,6-diphenyl-1-aza-3,6-diphosphacycloheptane; 5: 3,6-diphenyl-1-[(1R)-1-phenylpropyl]-1-aza-3,6-diphosphacycloheptane), with chiral exocyclic substituents at the nitrogen positions have been synthesized, with the prevailing formation of meso stereoisomers (P R P S ) as kinetically controlled products, by stereoselective condensation of 1,2-bis(phenylphosphanyl)ethane, formaldehyde and primary optically pure amines, namely (S)-(-)-1-phenylethylamine, (R)-(+)-1-phenylethylamine, (R)-(+)-1-phenylpropylamine, (R)-(+)-1-(4Ј-methoxyphenyl)ethylamine. The meso stereoisomers of bisphosphanes 3 RSS , 3-5 RSR readily form neutral and cationic P,P-chelate complexes 6-9 with platinum(II) (6:

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“…Thus, the meso isomers are chelating P,P-ligands, whereas the racemates are bridging ligands that form oligomeric metal complexes (Scheme 23). 46,50 Scheme 23…”

Section: Construction Of Macrocyclic Polyphosphinesmentioning

confidence: 99%

Phosphorus-containing macrocyclic compounds: synthesis and properties

Knyazeva¹,

Бурилов²,

Пудовик³

et al. 2013

Russ. Chem. Rev.

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Main trends in the development of methods for Main trends in the development of methods for the synthesis of phosphorus-containing macrocyclic com-the synthesis of phosphorus-containing macrocyclic compounds in the past 15 years are considered. Emphasis is pounds in the past 15 years are considered. Emphasis is given to reactions producing macrocyclic structures with the given to reactions producing macrocyclic structures with the participation of a phosphorus atom and other functional participation of a phosphorus atom and other functional groups involved in organophosphorus molecules and to groups involved in organophosphorus molecules and to modifications of macrocycles by phosphorus compounds modifications of macrocycles by phosphorus compounds in different valence states. Possibilities of the practical in different valence states. Possibilities of the practical application of phosphorus-containing macrocyclic com-application of phosphorus-containing macrocyclic compounds in difference areas of science and engineering are pounds in difference areas of science and engineering are discussed. The bibliography includes 205 references discussed. The bibliography includes 205 references. .

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1,3,6‐Azadiphosphacycloheptanes: A novel type of heterocyclic diphosphines

Abstract: The novel type

Cited by 37 publications

References 30 publications

Synthesis and unique reversible splitting of 14-membered cyclic aminomethylphosphines on to 7-membered heterocycles

Synthesis and unique reversible splitting of 14-membered cyclic aminomethylphosphines on to 7-membered heterocycles

Synthesis and Stereoselective Interconversion of Chiral 1‐Aza‐3,6‐diphosphacycloheptanes

Phosphorus-containing macrocyclic compounds: synthesis and properties

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