Contractive Annulation: A Strategy for the Synthesis of Small,Strained Cyclophanes and Its Application in the Synthesis of [2](6,1)Naphthaleno[1]paracyclophane

A new synthetic strategy (contractive annulation) for the synthesis of highly strained cyclophanes has been conceived and its viability has been demonstrated through a nine‐step synthesis of [2](6,1)naphthaleno[1]paracyclophane from [2.2]paracyclophane.     

Polymorphism versus thermochromism: interrelation of color and conformation in overcrowded bistricyclic aromatic enes

The nature of the thermochromic form of overcrowded bistricyclic aromatic enes (BAEs) has been controversial for a century. We report the single-crystal X-ray structure analysis of the deep-purple and yellow polymorphs of 9-(2,7-dimethyl-9H-fluoren-9-ylidene)-9H-xanthene (11), which revealed the molecules in a twisted and a folded conformation, respectively. Therefore, the deeply colored thermochromic form B of BAEs is identified as having a twisted conformation and the ambient-temperature form A as having a folded conformation. This relationship between the color and the conformation is further supported by the X-ray structures of the deep-purple crystals of the twisted 9-(9H-fluoren-9-ylidene)-9H-xanthene (10), and of the yellow crystals of the folded 9-(11H-benzo[b]fluoren-11-ylidene)-9H-xanthene (12). Based on this conclusive crystallographic evidence, eleven previously proposed rationales of thermochromism in BAEs are refuted. In the twisted structures, the tricyclic moieties are nearly planar and the central double bond is elongated to 1.40 A and twisted by 42 degrees . In the folded structures, the xanthylidene moieties are folded by 45 degrees and the fluorenylidene moieties by 18-20 degrees . Factors stabilizing the twisted and folded conformations are discussed, including twisting of formal single or double bonds, intramolecular overcrowding, and the significance of a dipolar aromatic "xanthenylium-fluorenide" push-pull structure.     

Regioselective formation of beta-alkyl-alpha-phenyliridabenzenes via unsymmetrical 3-vinylcyclopropenes: probing steric and electronic influences by varying the alkyl ring substituent

The synthesis of unsymmetrical (Z)-1-alkyl-3-(2-iodovinyl)-2-phenyl-1-cyclopropenes (R=Me (8 a), Et (8 b), iPr (8 c), and tBu (8 d)) and their reactions with Vaska's complex [Ir(CO)Cl(PPh3)2] and its trimethylphosphine analogue [Ir(CO)Cl(PMe3)2] were investigated. Iridabenzvalene (13/20), iridabenzene (14/21), and/or eta(5)-cyclopentadienyliridium complexes (15/22) were obtained in modest yields and were fully characterized by spectroscopic means. X-ray structural data was secured for iridabenzvalene 13 d and iridabenzenes 14 a,b,d. Whereas iridabenzenes 14 a-c were stable at 75 degrees C for 48 h, 14 d, which possesses a bulky tBu group, rearranged cleanly to cyclopentadienyliridium 15 d at 50 degrees C over 15 h and displayed first-order kinetics. The influence of the alkyl substituent on the mechanisms of iridacycle generation, isomerization, and iridabenzene regioselectivity is discussed.     

Experimental and Computational Studies of Anti‐Bredt Amidinium Salts

Experimental and computational investigations of anti‐Bredt amidinium salts are presented. Calculations show that the pyramidalization of an amino group can significantly destabilize the formal carbocation center of amidiniums, due to the decreased π donation. In some cases, the unfavorable ‐I effect of nitrogen surpasses its beneficial +M effect, and amidiniums become less stable than iminiums. It is shown that although 1‐aza‐3‐azonia[3.3.1]bicyclo‐non‐2‐enes can be isolated, they feature a nonclassical reactivity, which is more typical for iminium than amidinium salts, such as pronounced electrophilicity and azomethineylide instead of carbene formation.     

Quinoidal Oligo(9,10‐anthryl)s with Chain‐Length‐Dependent Ground States: A Balance between Aromatic Stabilization and Steric Strain Release

Quinoidal π‐conjugated polycyclic hydrocarbons have attracted intensive research interest due to their unique optical/electronic properties and possible magnetic activity, which arises from a thermally excited triplet state. However, there is still lack of fundamental understanding on the factors that determine the electronic ground states. Herein, by using quinoidal oligo(9,10‐anthryl)s, it is demonstrated that both aromatic stabilisation and steric strain release play balanced roles in determining the ground states. Oligomers with up to four anthryl units were synthesised and their ground states were investigated by electronic absorption and electron spin resonance (ESR) spectroscopy, assisted by density functional theory (DFT) calculations. The quinoidal 9,10‐anthryl dimer 1 has a closed‐shell ground state, whereas the tri‐ ( 2 ) and tetramers ( 3 ) both have an open‐shell diradical ground state with a small singlet–triplet gap. Such a difference results from competition between two driving forces: the large steric repulsion between the anthryl/phenyl units in the closed‐shell quinoidal form that drives the molecule to a flexible open‐shell diradical structure, and aromatic stabilisation due to the gain of more aromatic sextet rings in the closed‐shell form, which drives the molecule towards a contorted quinoidal structure. The ground states of these oligomers thus depend on the overall balance between these two driving forces and show chain‐length dependence.     

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 C₉₀H₄₈ 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°).     

Total Synthesis of Farnesin through an Excited‐State Nazarov Reaction

The asymmetric total synthesis of farnesin, a rearranged ent‐kaurenoid, was achieved through a convergent approach involving photo‐Nazarov and intramolecular aldol cyclizations to build the syn‐syn‐syn hydrofluorenol ABC ring system and bicyclo[3.2.1]octane CD ring system in the first application of a UV‐light‐induced excited‐state Nazarov cyclization of a non‐aromatic dicyclic divinyl ketone in a total synthesis. Unlike the conventional acid‐promoted ground‐state Nazarov reaction, the excited‐state Nazarov reaction enables stereospecific formation of the highly strained syn‐syn‐syn‐fused hydrofluorenone scaffold through a disrotatory cyclization.     

THROUGH-SPACE INTERACTION OF TETHERED GROUPS IN DIPHOSPHA PERI-SUBSTITUTED NAPHTHALENES

NMR properties of 1,8-diphosphanaphthalenes with prerequisites for strong through-space interaction were studied. The exceptional magnitude of ⁴J(PP) 246 Hz was found in Nap[P(NMe₂)₂][P(OMe)(NMe₂)] (Nap = naphthalene-1,8-diyl). The P^III, P^V mixed valence systems Nap[P(E)(OMe)₂][P(OMe)₂] (E = O, S, Se) show much lower magnitudes of through-space interaction than expected.     

The vorticity of the current density tensor and 3D-aromaticity

The induced current density ( J ( r )) vector field has been extensively used as a criterion of aromaticity and electron delocalization. However, the selection of the direction of the perturbing magnetic field ( B ) is arbitrary and in the case of three-dimensional electron delocalization/aromaticity the selection could be ambiguous. The J ( r ) has also recently received some criticism as an aromaticity index. We propose the Trace of the Vorticity of the Current Density tensor (TVCD) scalar field as a more suitable quantity for the evaluation of electron delocalization of three-dimensional systems. It does not depend on the orientation of B and contrary to other related scalar fields like the anisotropy of the induced current density, it does not lose the information of the direction of the currents. We show that not only the currents parallel to the molecular plane are important in the evaluation of the aromaticity, as is largely believed, but also the perpendicular ones, which information is included in the TVCD. The TVCD is very useful to study planar and 3D delocalized molecules (eg, fullerenes). Moreover, the integration of the TVCD over an internal surface of the 3D-cages serves as index for 3D-aromaticity.