A cascade reaction of indolyl-migratory isocyanide insertion, scaffold rearrangement and redox-neutral event with isocyanide as a C(sp3)H-N synthon efficiently constructs indolylisoindolinones.

Herein, we report a Pd(0)-catalyzed cascade reaction of intramolecular indolyl isocyanide-insertion, isocyanide-initiated scaffold-rearrangement with indolyl migration and redox-neutral process, which affords an efficient access to indolylisoindolinones. Isocyanide as a C(sp3)H-N synthon and the alkyl motif of isocyanide as a hydride source have been explored for the first time.

Evaluation of fluorine-mediated intermolecular interactions in tetrafluorinated tetrahydroisoquinoline derivatives: synthesis and computational studies.

Intermolecular interactions involving the aromatic C-F group in the absence of other strong hydrogen bond acceptors is the theme of this article. Weak interactions involving fluorine are known to generate various supramolecular synthons, thereby altering the crystal structures of small organic molecules. It is demonstrated that the weak interactions involving organic fluorine play a major role in directing crystal packing of highly flexible organic molecules like diphenyl tetrahydroisoquinolines reported herein. The intramolecular C-H...F hydrogen bonds are found to be significant in controlling the molecular conformation in specific cases wheras the intermolecular interactions involving the C-F groups result in a wide range of supramolecular synthons involving C-H...F and C-F...F-C interactions. The interactions are studied computationally to provide insight into their energies and the topology of the interactions is studied using Atoms in Molecules. C-H...F-C interactions are found to be quite stabilizing in nature with the stabilization energy of -13.9 kcal mol-1.

Quantitative characterization of new supramolecular synthons involving fluorine atoms in the crystal structures of di- and tetrafluorinated benzamides.

Strong hydrogen bonds play a significant role in crystal packing. In particular, the involvement of interactions involving fluorine in controlling the crystal packing requires appropriate attention, especially in the presence of other strong hydrogen bonds. In the present study, a detailed quantitative assessment has been performed of the nature, energetics and topological properties derived from the electron density in model compounds based on fluorinated benzamides (a total of 46 fluorine-substituted benzamides containing multiple fluorine atoms) in the solid state. The primary motivation in the design of such molecules is to enhance the acidity of the interacting H atoms in the presence of an increasing number of F atoms on the molecular scaffold, resulting in increased propensity towards the formation of intermolecular interactions involving organic fluorine. This exercise has resulted in the identification of new and frequently occurring supramolecular synthons involving F atoms in the packing of molecules in the solid state. The energetics associated with short and directional intermolecular Csp2-H...F-Csp2 interactions with significantly high electrostatic contributions is noteworthy, and the topological analysis reveals the bonding character of these ubiquitous interactions in crystal packing in addition to the presence of Csp2-F...F-Csp2 contacts.