Thermodynamic stability, structural and electronic properties for the C20-nAln heterofullerenes (n = 1-5): a DFT study.

DFT calculations are utilized to compare and contrast the substituted aluminum-heterofullerenes, C20-nAln (with n = 1-5) from thermodynamically view point, at density functional theory (DFT). Vibrational frequency analysis confirms that apart from C15Al5, all studied species are true minima. Considering the optimized geometries shows that all heterofullerenes are isolated-pentagon cage and none collapse to open deformed as segregated structure. The highest binding energy (5.56 eV/atom) and absolute heat of atomization (3323.68 kcal mol-1) reveals open-shell C19Al1 as the most stable thermodynamic heterofullerene. The most NICS (0) (isotropic and anisotropic parameters, -49.58 and - 46.47 ppm, respectively) introduces closed-shell C18Al2-2 as the most aromatic structure. Also, closed-shell C16Al4-1 heterofullerene emerges with the most polarizability (307.71 a.u.) and hence activity to interact with the surrounding polar species. The lowest and the highest charge transfer on the surfaces of C20 and C16Al4-2 without weak Al-Al bond, as the worst and the best candidate, respectively, provokes further investigation on impossible and possible application for hydrogen storage, respectively. We wish that the present survey will stimulate new experiments.

Intermolecular difunctionalization of alkenes: synthesis of ß-hydroxy sulfides.

Direct difunctionalization of carbon-carbon double bonds is one of the most powerful tools available for concomitant introduction of two functional groups into olefinic substrates. In this context, vicinal hydroxysulfenylation of unactivated alkenes has emerged as a novel and straightforward strategy for the fabrication of ß-hydroxy sulfides, which are extremely valuable starting materials in constructing various natural products, pharmaceuticals, and fine chemicals. The aim of this review is to summarize the most representative and important reports on the preparation of ß-hydroxy sulfides through intermolecular hydroxysulfenylation of the corresponding alkenes with special emphasis on the mechanistic features of the reactions.

Vicinal halo-trifluoromethylation of alkenes.

Both trifluoromethyl and halide groups are widely found in medicinally and pharmaceutically important compounds and, moreover, organohalides are commonly used as versatile intermediates in synthetic organic chemistry. Due to their prevalence and easy accessibility, alkene halo-trifluoromethylation provides a convenient way to install these valuable functionalities in complex targets. In this review, we summarize recent advances and achievements in this fast-growing research field. For clarity, the reactions were classified according to the type of halogen atom.

Direct sulfonamidation of (hetero)aromatic C-H bonds with sulfonyl azides: a novel and efficient route to N-(hetero)aryl sulfonamides.

N-Aryl sulfonamides belong to a highly important class of organosulfur compounds which are found in a number of FDA-approved drugs such as dofetilide, dronedarone, ibutilide, sotalol, sulfadiazine, sulfamethizole, vemurafenib, and many more. There is therefore continuing interest in the development of novel and convenient protocols for the preparation of these pharmaceutically important compounds. Recently, direct sulfonamidation of (hetero)aromatic C-H bonds with easily available sulfonyl azides has emerged as an attractive and powerful strategy to access N-(hetero)aryl sulfonamides where non-toxic nitrogen gas forms as the sole by-product. This review highlights recent advances and developments (2012-2020) in this fast growing research area with emphasis on the mechanistic features of the reactions.