Synthesis and Structural Properties of Adamantane‐Substituted Amines and Amides Containing an Additional Adamantane, Azaadamantane or Diamantane Moiety

Abstract

Introduction of adamantane moieties on diamondoids such as adamantane, 2‐azaadamantane or diamantane by amide formation and reduction to the corresponding amine was performed in a straightforward and easy way by amidation under Schotten–Baumann conditions and reduction with BH 3 ⋅ THF. The obtained amides and amines were studied in terms of structural properties towards the perspective of transformation into nanodiamonds. Crystal structure and dynamic NMR experiments of the most crowded amide obtained gave structural insights into the effect of bulkiness and steric strain on out‐of‐planarity of amide bonds (16.0°) and the kinetics and thermodynamics of amide bond rotation (ΔG ≠ 298K =11.5–13.3 kcal ⋅ mol −1 ).

Potential of Molecular Catalysts with Electron-Rich Transition Metal Centers for Addressing Long-Standing Chemistry Enigmas

“…Similar structures with remote interactions have been synthesized to adjust the basicity of metal oxide complexes and stabilize iron nitride complexes (see Figure ). − The metal is covalently bound to a carbon atom of a modified adamantane − ligand, which allows the presence of three OH groups in the vicinity of the metal pointing toward the metal as Pd – ···HO. It has been confirmed experimentally that the electron affinity of the group 10 transition metals M (M = Ni, Pd, Pt) increases by approximately 0.5 eV for every M – ···HOH interaction, implying the higher stability of the metal anion.…”

Exploring Structural and Spectroscopic Properties of Secondary Amide Derivatives Bearing Bulky and Hydrophilic Substituents

“…[11] As reported more recently by Bonsir et al, the introduction of adamantane fragments into the amide structure can offer enhanced properties and potentially lead to unique material functionalities as fluorescent nanodiamonds. [12] Characterizing the vibrational properties of amide compounds is crucial for understanding their structural features and hydrogen bonding interactions. [13] Vibrational spectroscopy, including infrared and Raman spectroscopy, provides valuable information about the stretching and bending vibrations of the amide functional group, usually referred to as "amide-band" vibrations.…”

“…reported several series of new adamantyl carboxamide derivatives (R 1 CONR 2 R 3 , R 1 =adamantyl, R 2 =H or Me, and R 3 =Aryl) with selective inhibitory action on the human enzyme 11β‐hydroxysteroid dehydrogenase type 1 [11] . As reported more recently by Bonsir et al ., the introduction of adamantane fragments into the amide structure can offer enhanced properties and potentially lead to unique material functionalities as fluorescent nanodiamonds [12] …”