Organocatalytic Asymmetric Synthesis of o-Carboranyl Amines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated (naphtho-)quinone methides as alkylating reagents suitable acid catalysts. This protocol also applicable S-alkylation 1-SH-o-C2B10H11. Control experiments kinetic studies provided important insights into reaction mechanism, which likely involves rate-determining generation quinone methide followed by fast enantio-determining nucleophilic addition.

Language: Английский

Synthesis, luminescent properties and application opportunities of С-substituted ortho-carborane π-conjugated luminophores: a mini review

Chimica Techno Acta, Journal Year: 2025, Volume and Issue: 12(2)

Published: April 2, 2025

The mini-review summarizes the recent achievements in synthesis of С-substituted o-carborane luminophores bearing an alkenyl- or alkynyl- π-conjugated system. main luminescence properties, such as absorbance, emission peaks, photophysical effects (particularly intramolecular charge transfer), local excitation, dual emission, and structure-property relationships are comprehensively studied. advantages diverse applications for this type cluster compounds organic light-emitting diodes (OLEDs), semiconductors, chemosensors, other components modern electronics extensively discussed. In addition, existing limitations chemical design application possibilities also considered.

Language: Английский

Self-Assembly and Dynamic Equilibrium of Trinuclear and Tetranuclear Cu(I) Supramolecules Featuring nido-Carborane-Supported N-Heterocyclic Carbene Ligands

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

The self-assembly of metallo-supramolecules has attracted considerable attention in recent decades. These discrete architectures are primarily driven by coordination interactions, typically involving M-N/O (Werner-type) or M-C (organometallic) bonding. However, the use M-π interactions for constructing these multinuclear complexes remains largely unexplored. In this work, we report trinuclear and tetranuclear copper(I) a combination interactions. Cu(I)-NHC were synthesized from nido-carborane-supported N-heterocyclic carbene (NHC) precursors Cu(I) ions. solution, dynamic equilibrium between species was observed, as confirmed variable-temperature NMR spectrum. Van't Hoff analysis revealed that is endothermic (ΔHeq = 53.6 kJ mol-1) entropically (ΔSeq 158 J mol-1 K-1). solid-state structures both forms elucidated through single-crystal XRD analysis. Density functional theory calculations showed Cu-CNHC bonds relatively weak (∼100 mol-1, approximately one-third strength typical bonds). This attributed to strong Coulombic attraction positively charged negatively nido-carborane ligands (M-π interactions), which significantly reduces bond neutral NHC moieties (M-C bonding).

Language: Английский