New P,N-Containing Cyclophanes with Exocyclic Pyridyl Containing Substituents on Phosphorus Atoms

Abstract

The synthesis of 28-and 36-membered P,N-containing cyclophanes with two 1,5-diaza-3,7-diphosphacyclooctane (17-21 %) whereas the condensations with the participation of 1,3-bis(4'-aminophenoxy) benzene containing three phenylene groups in the spacer are much less selective, and 36-membered cyclophanes have been obtained in low yields (7-9 %). It shows the strong influence of the starting phosphine nature on the selectivity of the Mannich-like condensation reactions. The treatment of 28-membered P-pyridylethyl substituted cyclophanes with hydrochloric acid in chloroform leads to the corresponding monohydrochlorides as a result of the protonation of pyridyl nitrogen atom, and in the solutions the fast migration of the proton between all pyridyl nitrogen centers is observed.Keywords: Macrocycle, cyclophane, pyridyl-containing phosphine, diamine, condensation, covalent self-assembly.Новые P,N -содержащие циклофаны с экзоциклическими пиридилсодержащими заместителями при атомах фосфора

First Example of Cage P4N4-Macrocycle Copper Complexes with Intracavity Location of Unusual Cu2I Fragments

“…The yields of P-pyridine-2-yl substituted cyclophanes 1 and 2 were moderate (23 and 15%, respectively) and noticeably lower than the yields of analogous P-aryl substituted macrocycles (18–60%) [ 22 ], but close to the yields of 28-membered P-(2-(pyridine-2′-yl)ethyl) substituted macrocycles (17–21%) [ 32 ]. The elemental analysis, mass spectrometry, 31 P and 1 H NMR spectroscopy data of compounds 1 and 2 are consistent with their cyclophane structures which include two 1,5-diaza-3,7-diphosphacyclooctane rings.…”

“…The elemental analysis, mass spectrometry, 31 P and 1 H NMR spectroscopy data of compounds 1 and 2 are consistent with their cyclophane structures which include two 1,5-diaza-3,7-diphosphacyclooctane rings. The proton signals of the P-CH 2 -N fragments of both compounds appear to be typical (AB) 2 X systems for the chair–chair conformation of the heterocyclic eight-membered fragments with the equatorial positions of substituents at the phosphorus atoms and the axial positions of their lone electron pairs, namely, two doublets of doublets with the values of the coupling constants 2 J HH = 15.0–15.1 Hz and 2 J PH = 9.7–10.5 Hz for equatorial protons and 5.6–5.7 Hz for axial protons [ 22 , 23 , 32 ]. These structures are typical for 28-membered 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphanes where the phenylene rings and 1,5-diaza-3,7-diphosphacyclooctanes form a truncated rhombohedral prism [ 22 , 32 ], and the conformation of diphosphine fragments is favorable for the formation of bis-P,P-chelate metal complexes.…”

“…The conformation of the macrocyclic ligand in complex 3 is only slightly distorted as compared with typical cylindrical conformations of uncoordinated 1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphanes [ 22 , 32 ]. The chelating 1,5-diaza-3,7-diphosphacyclooctane fragments maintain the starting chair–chair conformation in contrast to the previously described metal complexes of similar P,N-containing cyclophanes with longer tri- and tetraphenylene phane fragments where the chelating diphosphine rings adopt a chair–boat conformation [ 26 , 27 ].…”

Phospha-Mannich reactions of RPH2, R2PH, and R3P

“…59 [14] -53.5 (C 6 D 6 ), -49.8 and -53.0 (CDCl 3 ) CH 2 21 [125] -51.7 (DMF) CH 2 17 [126,127] -55.9 (CDCl 3 ) CH 2 23 [127] -45.7 (DMSO-d 6 ) S 42 [125] -50.5 (DMF) S 21 [125] -46.3 (DMF) S 60 [125] -41.5 (DMF) S 21 [126,127] -52.8 (DMSO-d 6 ) 10 S 15 [127] -44.0 (DMSO-d 6 )…”

“…Entry Spacer R Yield, % d P , ppm 53 [14] -44.4 (CDCl 3 ) 80 [14] -48.8 (CDCl 3 ) 43 [14] -52.8 (DMSO-d 6 ) 9 [126,127] -45.6 (DMSO-d 6 ) 7 [126,127] -56.4 (DMSO-d 6 ) 10-44 [129] -43 [14] -50.9 (DMSO-d 6 ) 49 [14,130] -40.9 (CDCl 3 ) 42 [14,130] -45.5 (CDCl 3 ), -46.9 (C 6 D 6 ) 10-44 [129] -15 [127,131] Table S15. Bicyclic P2,N2-acetals, obtained by reactions of 1,2-diphosphinobenzene or 1,2diphosphinoethane with CH2O and primary amines.…”