Aromaticity in Semi-Condensed Figure-Eight Molecules.

Electron delocalization and aromaticity was comparatively evaluated in recently synthesized figure-eight molecules made of two condensed U-shaped polycyclic aromatic hydrocarbon moieties connected either by two single bonds or by two para-phenylene groups. The selected examples include molecules that incorporate eight-membered and sixteen-membered rings, as well as a doubly [5]helicene-bridged (1,4)cyclophane. We probe whether some electron delocalization could occur through the stereogenic single bonds in these molecules: Is aromaticity purely (semi-)local, or possibly also global in these molecules? It was concluded that the situation can go from a purely (semi-)local character when the dihedral angle at the connecting single bonds is large, such as in biphenyl, to a predominantly (semi-)local character with a minor global contribution when the dihedral angle is small, such as in the para-phenylene connectors of the [5] helicene-bridged cyclophane.

Helicene Aromaticity Deviates from the Clar Rule-On the Electronic Dissimilarity of Large Isomeric Fibonacenes.

This combined experimental and theoretical study illustrates the profound consequences of non-planarity on the electronic properties of polycyclic arenes. Three isomeric [10]fibonacene tetraesters were synthesized through a robust and regiocontrolled Perkin/Mallory approach: a nearly planar [10]phenacene derivative, a moderately twisted [10]semicircle derivative, and a 3D non-planar [10]helicene derivative. The photophysical properties of the 3D [10]helicene isomer were found to be dramatically different from the comparable ones of the [10]phenacene and [10]semicircle isomers. The aromatic properties of the [10]phenacene and [10]semicircle isomers conform well with their predictive Kekulé and Clar analyses, but the [10]helicene isomer deviates from these general topological rules, which appears to be a general phenomenon for [n]fibonacenes with n≥9.

Conformational, Structural, and Chiroptical Properties of an Overcrowded Triply Fused Carbo[7]helicene.

Recently, the synthesis of the racemate of an overcrowded triply fused carbo[7]helicene of formula C66H36 with three carbo[7]helicenes fused within a central six-membered ring was described. This molecule was found to embed an extremely contorted central six-membered ring and two negative curvatures. We report herein the resolution of the corresponding enantiomers and their conformational, structural, photophysical, and chiroptical properties. The racemization of the triply fused carbo[7]helicene was determined to proceed at a rate of krac = 8.06 × 10-4 s-1 at 175 °C in ortho-dichlorobenzene, corresponding to a barrier to enantiomerization ΔGenant‡ = 140.4 kJ·mol-1, a value significantly lower than for pristine carbo[7]helicene. Interestingly, the crystalline structures of the racemic and enantiopure materials show some differences regarding the molecular geometry, with an increased negative curvature in the latter cases. This unusual curved delocalized π-conjugated system afforded notably green fluorescence at room temperature and far-red phosphorescence at low temperature. Finally, electronic circular dichroism and circularly polarized luminescence responses of the enantiopure compounds have been measured and showed very close absorption and emission dissymmetry factors, gabs and glum, respectively, of ca. 2.6 × 10-3, indicating a similar chiral rigid geometry for both ground and excited states.

Overcrowded Triply Fused Carbo[7]helicene.

This paper presents the synthesis and comprehensive analysis of a highly contorted and doubly negatively curved multihelicene compound, composed of three carbo[7]helicene units fused within a central six-membered ring. The synthesis of this compound involved a [2 + 2 + 2] cycloaddition reaction of 13,14-picyne, employing a Ni(0) catalyst, which exhibited superior performance compared to conventional Pd(0) catalysts. The evaluation of aromaticity in this triple carbo[7]helicene, utilizing magnetic and electronic criteria, led to noteworthy insights challenging the limitations of Clar's model of aromaticity.

A Triply [5]Helicene-Bridged (1,3,5)Cyclophane.

A rigid propeller-shaped conjugated triple macrocycle consisting of two nearly perfectly stacked benzene rings and three linking [5]helicene moieties has been synthesized using a glyoxylic Perkin approach. Analysis of the electron delocalization in this atypical aromatic molecule revealed global aromaticity and a 78 π-electron circuit along the edge of its triple loop, to the detriment of the two 6 π-electron circuits in the two stacked benzene rings.

Aryne Atropisomers: Chiral Arynes for the Enantiospecific Synthesis of Atropisomers and Nanographene Atropisomers.

The basics about arynes and their applications in synthetic organic chemistry are briefly presented, and the concept of atropisomerism is defined, highlighting that it is a time-dependent form of isomerism and chirality. It is remembered that racemization is a macroscopic and statistical irreversible process, while enantiomerization is a nanoscopic reversible process that occurs at the molecular scale, with racemization being twice as fast as enantiomerization. The concept of aryne atropisomers is introduced with a naive question: Can synthetically useful nonracemic aryne atropisomers having a triple bond ortho to the stereogenic single bond exist in solution? It was found that such aryne atropisomers can be generated in solution from easily available ortho-iodoaryl triflate precursors and excess trimethylsilylmethylmagnesium chloride. Analysis of the barriers to enantiomerization of some aryne atropisomers by computational modeling revealed the key contribution to the configurational stability of the H atom in tris-ortho-substituted biphenyl-based atropisomers. Using a specially designed prototype of aryne atropisomer, for which the barrier to enantiomerization was accurately evaluated by advanced computational modeling, the kinetic parameters of its reaction with furan were experimentally determined. From these measurements, it was concluded that any aryne atropisomer with a barrier to enantiomerization ΔGenant⧧ equal to or higher than 50 kJ mol-1 would lead to fully enantiospecific reactions. The synthetic applications of two structurally distinct aryne atropisomers built on a 1-phenylnaphthalene platform are described: one has the aryne triple bond embedded in the naphthyl moiety, and the other has the aryne triple bond embedded in the phenyl moiety. Both aryne atropisomers allowed for the fully enantiospecific, and possibly overall enantioselective, syntheses of original atropisomers based on standard aryne chemistry. For instance, reactions with anthracene and perylene afforded triptycene and nanographene atropisomers, respectively, in high enantiomeric excesses. A bis(aryne) atropisomer synthetic equivalent prepared from either enantiomer of BINOL is described for 3D bidirectional reactions with a single handedness. Its 2-fold reactions with anthracene and perylene afforded the corresponding severely congested bis(benzotriptycene) (99% ee) nanocarbon atropisomer and bis(anthra[1,2,3,4-ghi]perylene) (98% ee) nanographene atropisomer, respectively. This allowed the discovery of bis(twistacene) atropisomers as a new class of polycyclic aromatic hydrocarbons (PAH) with multiple stereogenicities. Cross reactions with the bis(aryne) atropisomer synthetic equivalent and two different arynophiles proved feasible, providing a nanographene atropisomer with a benzotriptycene unit and an anthra[1,2,3,4-ghi]perylene unit assembled around a stereogenic axis as a unique chiral PAH (99% ee). Overall, because the concept is simple and its implementation is easy, aryne atropisomers is an attractive approach to the synthesis of atropisomers in a broad meaning. Applications to the synthesis of large PAH atropisomers with single handedness are particularly promising.

Synthesis, Photophysical Properties, and Aromaticity of Pyrazine-Fused Tetrazapentalenes.

Pyrazine-fused 1,2,6,6a-tetrazapentalenes (PyTeAP) are zwitterionic tricyclic compounds exhibiting an original pattern with four consecutive nitrogen atoms. They were obtained by a challenging cyclization through the formation of a N-N bond under thermolytic conditions. Ten derivatives were synthesized, and the original scaffold of PyTeAP was confirmed by single-crystal X-ray diffraction analysis of one derivative. Examination of their photophysical properties in solution revealed blue fluorescence with λem = 416-426 nm. Theoretical investigations of the aromaticity in these compounds through magnetic criteria evidenced the presence of a dominant 14-electron circuit at the periphery.

Enantiospecific Syntheses of Congested Atropisomers through Chiral Bis(aryne) Synthetic Equivalents.

The synthetic equivalents of the enantiopure binaphthyl bis(aryne) atropisomers derived from BINOL (1,1'-bi-2,2'-naphtol) featuring a stereogenic axis vicinal to the two reactive triple bonds can be generated for the first time in solution in an enantiospecific manner. Using a two-step sequence based on the bidirectional [4+2] cycloaddition of furan derivatives followed by an aromatizative deoxygenation reaction, several 9,9'-bianthracenyl-based atropisomers could be prepared enantiospecifically in high enantiomeric purity. Alternatively, bidirectional reactions with anthracene, 2-bromostyrene, and perylene as the arynophiles afforded very congested bis(benzotriptycene), bis(tetraphene) and bis(anthra[1,2,3,4-ghi]perylene) nanocarbon atropisomers in equally high enantiomeric purity. In complement, cross reactions with two different arynophiles revealed possible. The unusual atropisomer prototypes described in this study open the way to enantiopure nanographene atropisomers designed for functions.

Determination of the Rate Constant of the [4 + 2] Cycloaddition Between an Aryne Atropisomer and Furan in Solution.

Using a specially designed prototype of a nonracemic aryne atropisomer with a low barrier to enantiomerization (ca. 36 kJ·mol-1), it was possible to determine the kinetic constant of its cycloaddition with furan in solution by a combination of theoretical calculations and experimental measurements. It was found that the reaction half-life of this aryne atropisomer in solution with 100 equivalents of furan as the trapping reagent is <150 ns at temperatures above -20 °C.

Visualizing electron delocalization in contorted polycyclic aromatic hydrocarbons.

Electron delocalization in contorted polycyclic aromatic hydrocarbon (PAH) molecules was examined through 3D isotropic magnetic shielding (IMS) contour maps built around the molecules using pseudo-van der Waals surfaces. The resulting maps of electron delocalization provided an intuitive, yet detailed and quantitative evaluation of the aromatic, non aromatic, and antiaromatic character of the local and global conjugated cyclic circuits distributed over the molecules. An attractive pictural feature of the 3D IMS contour maps is that they are reminiscent of the Clar π-sextet model of aromaticity. The difference in delocalization patterns between the two faces of the electron circuits in contorted PAHs was clearly visualized. For π-extended contorted PAHs, some splits of the π system resulted in recognizable patterns typical of smaller PAHs. The differences between the delocalization patterns of diastereomeric chiral PAHs could also be visualized. Mapping IMS on pseudo-van der Waals surfaces around contorted PAHs allowed visualization of their superimposed preferred circuits for electron delocalization and hence their local and global aromaticity patterns.

Unbalanced 2D Chiral Crystallization of Pentahelicene Propellers and Their Planarization into Nanographenes.

The chiral self-assembly of trispentahelicene propellers on a gold surface has been investigated in ultrahigh vacuum by means of scanning tunneling microscopy and time-of-flight secondary ion mass spectrometry. The trispentahelicene propellers aggregate into mirror domains with an enantiomeric ratio of 2 : 1. Thermally induced cyclodehydrogenation leads to planarization into nanographenes, which self-assemble into closed-packed layers with two different azimuths. Further treatment induces in part dimerization and trimerization by intermolecular cyclodehydrogenation.

Periselectivity in the Aza-Diels-Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study.

Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.

Enantiospecific Generation and Trapping Reactions of Aryne Atropisomers.

Enantioenriched aryne atropisomers having a biaryl stereogenic axis vicinal to the reactive triple bond are demonstrated to exist. These reaction intermediates are easily produced in situ and can undergo the standard aryne cycloaddition chemistry in an enantiospecific manner. Notably, the aryne atropisomers herein have allowed the practical syntheses of a small nanographene as well as some triptycene and anthracene derivatives that embed stereogenic axes of controlled absolute configurations.

Periselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and N-(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study.

The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes, in situ derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and N-(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the N-(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the N-(5-pyrazolyl)imines as the 2π partners at their C═N double bond. A computational modeling study using DFT methods allowed rationalizing this change of periselectivity: the formation of spiro hydropyridin-4-ones is under thermodynamic control while the formation of 1,3-oxazin-4-ones is kinetically controlled, and slightly thermodynamically disfavored in the five-membered ring series. The competing cyclodimerization of the α-oxoketenes is also studied in detail.

Stereoselective Syntheses, Structures, and Properties of Extremely Distorted Chiral Nanographenes Embedding Hextuple Helicenes.

We report a molecular design and concept using π-system elongation and steric effects from helicenes surrounding a triphenylene core toward stable chiral polycyclic aromatic hydrocarbons (PAHs) with a maximal π-distortion to tackle their aromaticity, supramolecular and molecular properties. The selective syntheses, and the structural, conformational and chiroptical properties of two diastereomeric large multi-helicenes of formula C90 H48 having a triphenylene core and embedding three [5]helicene units on their inner edges and three [7]helicene units at their periphery are reported based on diastereoselective and, when applicable, enantiospecific Yamamoto-type cyclotrimerizations of racemic or enantiopure 9,10-dibromo[7]helicene. Both molecules have an extremely distorted triphenylene core, and one of them exhibits the largest torsion angle recorded so far for a benzene ring (twist=36.9°).

Synthesis of Pyrrolo[2,3-c]isoquinolines via the Cycloaddition of Benzyne with Arylideneaminopyrroles: Photophysical and Crystallographic Study.

An efficient and quick access toward a series of (E)-2-arylideneaminopyrroles 6 and to their benzyne-promoted aza-Diels-Alder cycloaddition products is provided. These products are three pyrrolo[2,3-c]isoquinolines 8a-c substituted in position 5 with different electron-acceptor (A) or electron-donor (D) aryl groups. Intermediates and products were obtained in good yields (up to 78 and 84%, respectively), and their structures were determined on the basis of NMR measurements and HRMS analysis. Photophysical properties of 8a-c were investigated, finding good Stokes shift in different solvents, but only the product 8c showed appreciable fluorescence intensity since its 5-aryl group (2,4-Cl2Ph) could favor the twisted intramolecular charge transfer effect. In addition, a riveting relationship between solvent viscosity and fluorescence intensity was found. Structures of 6 and 8 were studied and confirmed by single-crystal X-ray diffraction, observing that their electronic distributions effect the supramolecular assembly but with only long-distance hydrophobic interactions. A CE-B3LYP model was used to study the energetic topology and understand the crystal architecture of compounds as well as find a connection with both the synthetic and photophysical results.

Cyclobishelicenes: Shape-Persistent Figure-Eight Aromatic Molecules with Promising Chiroptical Properties.

Cyclobis[n]helicenes (n=3 or 5) are chiral D2 -symmetric π-conjugated macrocycles with stable lemniscular, or figure-eight, shapes. The conformational analysis of five different cyclobis[n]helicenes revealed that these molecules can only exist as their lemniscular conformers with high barriers to enantiomerization (>200 kJ mol-1 ). The enantiomers of a cyclobis[5]helicene were resolved by HPLC and their unusual chiroptical properties were attributed to the inherent chirality of their macrocyclic figure-eight.

Enantioselective Organocatalytic Four-Atom Ring Expansion of Cyclobutanones: Synthesis of Benzazocinones.

An enantioselective Michael addition- four-atom ring expansion cascade reaction involving cyclobutanones activated by a N-aryl secondary amide group and ortho-amino nitrostyrenes has been developed for the preparation of functionalized eight-membered benzolactams using bifunctional aminocatalysts. Taking advantage of the secondary amide activating group, the eight-membered cyclic products could be further rearranged into their six-membered isomers having a glutarimide core under base catalysis conditions without erosion of optical purity, featuring an overall ring expansion- ring contraction strategy.

Normal, Abnormal, and Cascade Wittig Olefinations of α-Oxoketenes.

α-Oxoketenes generated in situ by a thermal Wolff rearrangement have been found to participate as 1,2- and 1,4-ambident C-electrophilic/O-nucleophilic reagents towards donor/acceptor carbonyl-stabilized Wittig ylides. This resulted in the very direct and practical syntheses of functionalized allenes by a normal Wittig olefination, 4H-pyran-4-ones by an abnormal Wittig olefination, or 4H-pyranylidenes following a Wittig/abnormal Wittig cascade sequence as a function of the substrates combination employed. Mechanistic experimental and computational studies provided a full rational for these reactivity switches. Some unusual mechanistic features for Lewis acid-free Wittig olefinations were identified in this series such as the involvement of betaine intermediates and some degree of reversibility in the normal Wittig olefination. The abnormal Wittig olefination was fully uncovered.

Chiral Nanographene Propeller Embedding Six Enantiomerically Stable [5]Helicene Units.

A one-step synthesis of a nanographene propeller with a D3-symmetry was obtained starting from 7,8-dibromo[5]helicene by Yamamoto nickel(0) couplings. It afforded a chiral polyaromatic hydrocarbon (PAH) embedding six enantiomerically stable [5]helicene units. This dense accumulation of helical strain resulted in a distorted geometry, but stable stereochemistry. The conformational, structural, chiroptical, and photophysical properties of the molecule are reported.