Several fully π-conjugated macrocycles with puckered or cage-type structures were recently found to exhibit aromatic character according to both experiments and computations. We examine their electronic structures and put them in relation to 3D-aromatic molecules (e.g., closo-boranes) and to 2D-aromatic polycyclic aromatic hydrocarbons. Using qualitative theory combined with quantum chemical calculations, we find that the macrocycles explored hitherto should be described as 2D-aromatic with three-dimensional molecular structures (abbr. 2D-aromatic-in-3D) and not as truly 3D-aromatic. 3D-aromatic molecules have highly symmetric structures (or nearly so), leading to (at least) triply degenerate molecular orbitals, and for tetrahedral or octahedral molecules, an aromatic closed-shell electronic structure with 6n + 2 electrons. Conversely, 2D-aromatic-in-3D structures exhibit aromaticity that results from the fulfillment of Hückel's 4n + 2 rule for each macrocyclic path, yet their π-electron counts are coincidentally 6n + 2 numbers for macrocycles with three tethers of equal lengths. It is notable that 2D-aromatic-in-3D macrocyclic cages can be aromatic with tethers of different lengths, i.e., with π-electron counts different from 6n + 2, and they are related to naphthalene. Finally, we identify tetrahedral and cubic π-conjugated molecules that fulfill the 6n + 2 rule and exhibit significant electron delocalization. Yet, their properties resemble those of analogous compounds with electron counts that differ from 6n + 2. Thus, despite the fact that these molecules show substantial π-electron delocalization, they cannot be classified as true 3D-aromatics.

Optically pure alcohols are abundant in nature and attractive as feedstock for organic synthesis but challenging for further transformation using atom efficient and sustainable methodologies, particularly when there is a desire to conserve the chirality. Usually, substitution of the OH group of stereogenic alcohols with conservation of chirality requires derivatization as part of a complex, stoichiometric procedure. We herein demonstrate that a simple, inexpensive, and environmentally benign iron(III) catalyst promotes the direct intramolecular substitution of enantiomerically enriched secondary and tertiary alcohols with O-, N-, and S-centered nucleophiles to generate valuable 5-membered, 6-membered and aryl-fused 6-membered heterocyclic compounds with chirality transfer and water as the only byproduct. The power of the methodology is demonstrated in the total synthesis of (+)-lentiginosine from D-glucose where iron-catalysis is used in a key step. Adoption of this methodology will contribute towards the transition to sustainable and bio-based processes in the pharmaceutical and agrochemical industries.

The first hydrogenation step of benzene, which is endergonic in the electronic ground state (S₀), becomes exergonic in the first triplet state (T₁). This is in line with Baird’s rule, which tells that benzene is antiaromatic and destabilized in its T₁state and also in its first singlet excited state (S₁), opposite to S₀, where it is aromatic and remarkably unreactive. Here we utilized this feature to show that benzene and several polycyclic aromatic hydrocarbons (PAHs) to various extents undergo metal-free photochemical (hydro)silylations and transfer-hydrogenations at mild conditions, with the highest yield for naphthalene (photosilylation: 21%). Quantum chemical computations reveal that T₁-state benzene is excellent at H-atom abstraction, while cyclooctatetraene, aromatic in the T₁and S₁states according to Baird’s rule, is unreactive. Remarkably, also CVD-graphene on SiO₂is efficiently transfer-photohydrogenated using formic acid/water mixtures together with white light or solar irradiation under metal-free conditions.

Benzene exhibits a rich photochemistry which can provide access to complex molecular scaffolds difficult to access with reactions in the electronic ground state. While benzene is aromatic in its ground state it is antiaromatic in its lowest ππ* excited states. Herein, we clarify to what extent relief of excited state antiaromaticity (ESAA) triggers a fundamental benzene photoreaction: the photoinitiated nucleophilic addition of solvent to benzene in acidic media leading to substituted bicyclo[3.1.0]hex-2-enes. The reaction scope was probed experimentally and it was found that silyl substituted benzenes provide the most rapid access to bicyclo[3.1.0]hexene derivatives, formed as single isomers with three stereogenic centers in yields up to 75% in one step. Two major mechanism hypotheses, both involving ESAA relief, were explored through quantum chemical calculations and experiments. The first mechanism involves protonation of excited state benzene and subsequent rearrangement to bicyclo[3.1.0]hexenium cation, trapped by a nucleophile, while the second involves photorearrangement of benzene to benzvalene followed by protonation and nucleophilic addition. Our studies reveal that the second mechanism is operative. We also clarify that similar ESAA relief leads to puckering of S1 state silabenzene and pyridinium ion, where the photorearrangement of the latter is of established synthetic utility. Finally, we identified causes for the limitations of the reaction, information that should be valuable in explorations of similar photoreactions. Taken together, we reveal how the ESAA in benzene and 6π-electron heterocycles trigger photochemical distortions that provide access to complex three-dimensional molecular scaffolds from simple reactants.