Suzuki aryl cross-coupling chemistry using derivatives of 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane

An exploration into the scope of Suzuki aryl cross-coupling chemistry using derivatives of 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane is reported. The coupling of 4-iodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane with various aryl boronic acids and boronic acid pinacol esters was successful, with the exception of very sterically demanding systems, such as mesityl. The synthesis of the previously unreported 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophanyl-4-boronic acid is described, together with various Suzuki aryl cross-coupling reactions of this new system. Using standard Suzuki methodology, it was possible to prepare dicyclophanes bearing two octafluoro[2.2]paracyclophane units separated by both one and two benzene rings.     

4,5-dehydro- and 4,5,15,16-bis(dehydro)octafluoro[2.2]paracyclophanes: facile generation and extraordinary Diels-Alder reactivity

Dehydroiodination of 4-iodo- and 4,15-diiodo-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane by treatment with KO(t)Bu in the presence of benzene, naphthalene, anthracene, and [2.2]paracyclophane affords each of the corresponding Diels-Alder mono- and bis-cycloadducts derived from the presumed aryne intermediates in high yield. Monoadducts of t-butylbenzene and furan are also obtained in excellent yield. All of the products were characterized by their NMR spectra, with four of them also being confirmed by X-ray crystallography. The extraordinary selectivity/reactivity of the aryne intermediate is discussed.     

2.2]paracyclophane/dehydroannulene hybrids: probing the aromaticity of the dehydro[14]annulene framework

The synthesis of [2.2]paracyclophane/dehydro[14]annulene hybrids 1 and 2 is reported. Comparison of the proton NMR spectra of 1 and 2 with their open precursors and with related model compounds reveals the pronounced effect of macrocycle formation upon the cyclophane protons H15/H16, which lie above the shielding cone of the diatropic [14]annulene moiety. [structure: see text]     

Ethynyl[2.2]paracyclophanes and 4-isocyano[2.2]paracyclophane as ligands in organometallic chemistry

An alternative synthesis of (±)-4-ethynyl[2.2]paracyclophane (PCPCCH) (5) and 4,16-diethynyl[2.2]paracyclophane (6) via the Corey-Fuchs reaction has been developed. The olefinic intermediate 4-dibromovinyl[2.2]paracyclophane (3) has been isolated and structurally characterized. The racemic terminal alkyne 5 was employed as starting material for assembling of a luminescent extended π-conjugated system containing a thiophene unit and for a catalytic bis-silylation reaction yielding the olefinic dithioether Z-PhSCH₂Me₂SiC(H)C(PCP)SiMe₂CH₂SPh (9). The dimetallatetrahedran [Co₂(CO)₆(μ-η²-PCP-CCH)] (10) has been prepared and its crystal structure determined by an X-ray diffraction analysis. Alkyne 5 has also been used for the preparation of the Pt(0) complex [Pt(PPh₃)₂(PCPCCH)] (11) and the heterodinuclear dimetallacyclopentenone [(OC)₂Fe{μC(O)C(PCP)C(H)}(μ-dppm)Pt(PPh₃)] (12). The synthesis and reactivity of 4-isocyano[2.2]paracyclophane (15) towards heterobimetallic iron-platinum and palladium-platinum complexes is also presented. Opening of the dative iron → platinum bond of [(OC)₄Fe(μ-dppm)PtCl₂] (16) occurred upon addition of 15 to a CH₂Cl₂ solution of 16 leading to [(OC)₄Fe{μ-dppm}PtCl₂(CNPCP)] (17). Treatment of [ClPd(μ-dppm)₂PtCl] (18) with isocyanide 15 in a 1:1 ratio affords the A-frame compound [ClPd(μ-dppm)₂(μ-CNPCP)PtCl] (19), resulting from formal insertion of 15 into the Pd-Pt bond. Addition of 2 equiv. of 15-18 leads to the ionic A-frame compound [ClPd(μ-dppm)₂(μ-CNPCP)Pt(CNPCP)]Cl (20).     

A preparative microwave method for the isomerisation of 4,16-dibromo[2.2]paracyclophane into 4,12-dibromo[2.2]paracyclophane

4,16-Dibromo[2.2]paracyclophane (4) is isomerised to 4,12-dibromo[2.2]paracyclophane (1) by the application of microwaves in DMF solution.     

Synthesis of perfluoro[2.2]paracyclophane

A synthesis of perfluoro[2.2]paracyclophane has been sought ever since the partially fluorinated octafluoro[2.2]paracyclophane (AF4) was prepared and its chemistry studied. This compound has now been prepared in 39% yield from the precursor, 1,4-bis(chlorodifluoromethyl)-2,3,5,6-tetrafluorobenzene by its reaction with Zn when heated in acetonitrile at 100 degrees C. Two preparations of the precursor, first from 1,4-dicyano-2,3,5,6-tetrachlorobenzene and an improved method beginning from 1,2,4,5-tetrachlorobenzene, are also described as are key comparisons to our related synthesis of AF4.     

Nitrosonium complexes of [2.2]paracyclophane

The reaction of [2.2]paracyclophane with nitrosonium tetrachloroaluminate was studied by NMR (¹H, ¹³C) spectroscopy using deuterium isotopic perturbation technique. The resulting cationic complexes containing one and two nitrosonium ions are involved in fast (on the NMR time scale) interconversion. Quantum-chemical calculations performed on the DFT level (using triple zeta basis set) indicate the higher stability of 2η single-charged π-complexes relative to σ complexes corresponding to the addition of NO⁺ ion at the ipso and ortho positions. The formation of the single-charged π-complex is energetically more favorable, compared to the double-charged π-complex. The affinity of NO⁺ for [2.2]paracyclophane is much greater than for p-xylene, presumably due to stacking interaction between the aromatic rings in the π-complex.     

The first synthesis and characterization of both diastereomers of a di[2.2]paracyclophane: 4,4'-bis(1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane)

The synthesis and characterization of both diastereomers of a system comprised of two [2.2]paracyclophane units linked through a single 4,4' bond are described. Both the meso and d,l diastereomers of 4,4'-bis(octafluoro[2.2]paracyclophane) have been prepared via a palladium-catalyzed reductive homocoupling reaction by copper, producing a 3:2 ratio of meso and d,l diastereomers. A similar reductive homocoupling of pseudo-o-iodotrifluoromethyloctafluoro[2.2]paracyclophane gave only the analogous meso diastereomer. Single-crystal X-ray structures were obtained for all of the diparacyclophane products.     

An exploration of Suzuki aryl cross coupling chemistry involving [2.2]paracyclophane derivatives

Suzuki aryl cross coupling reactions using derivatives of [2.2]paracyclophane were examined. A variety of aryl boronic acids and pinacolate esters were successfully cross coupled with 4-bromo[2.2]paracyclophane under standard Suzuki conditions. Whilst an excellent tolerance for electron donating and withdrawing groups was observed, cross coupling reactions with highly sterically demanding borates (e.g. mesityl) were unsuccessful. The preparation and stability of the previously unreported [2.2]paracyclophanyl-4-boronic acid, -pinacolate ester and -dimethyl ester are described, along with the utility of these systems in Suzuki aryl cross coupling reactions. Application of this methodology led to a dicyclophane containing two [2.2]paracyclophane units separated by a 4-4' connected biphenyl spacer group.     

Novel iron complexes of [2.2]paracyclophane

The synthesis of [2.2]paracyclophane-iron complexes $\text{4}$ (R=H or Me) is described.     

Ruthenium clusters containing the [2.2] paracyclophane ligand: Recent developments in arene-cluster chemistry

In this article we review the synthesis, reactivity, and characterization of a number of clusters bearing the [2.2] paracyclophane ligand with nuclearities ranging from two to eight. Particular attention is focused on the different coordination modes that paracyclophane adopts; these being µ₁- ⁶, µ₂- ³ : ³, µ₃- ¹ : ² : ², and µ₃- ² : ² : ². Structural modifications which take place within the ring system on bonding in these various modes are also discussed.     

Molecular structure of 4,15-dibromo[2.2]paracyclophane

An x-ray structural study has shown that the nature of the steric distortions in [2,2]paracyclophane remains practically unchanged when Br-substituents are introduced into positions 4 and 15.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 588–590, March, 1990.     

Spatial ring current model of the [2.2]paracyclophane molecule

A representation of the current density induced in the [2.2]paracyclophane molecule by a homogeneous magnetic field parallel to the line joining the centers of the phenylene rings is given in compact form by a stagnation graph that conveys essential information. Analogous graphs were obtained for two perpendicular directions. Plots of streamlines are also reported to complete a ring current model that has been proved useful to understand the magnetropicity of the system. Stagnation graphs, maps of streamlines and moduli of the current density, and plots of Biot-Savart magnetic shielding density provide a basic tool kit for rationalizing magnetic response of complex systems.     

Phane properties of [2.2]paracyclophane/dehydrobenzoannulene hybrids

A series of [2.2]paracyclophane/dehydrobenzo[14]annulene (PC/DBA) hybrids (hydrocarbons 5, 6, 9, 10 b, and 10 c), [2.2]paracyclophane/dehydro[14]annulene (PC/DA) hybrids (7 and 8) and suitable model systems (11, 12, and 33) has been synthesized. Comparison of the electronic absorption spectra in each series of compounds provides further insight into the global communication between the decks in the [2.2]paracyclophane unit.