Azaindenocorannulenes: Synthesis, Properties, and Chirality

Xiaoqi Tian (1) , Loïc M Roch (2) , Nicolas Vanthuyne (3) , Jun Xu (1) , Kim K Baldridge (1) , Jay S Siegel (1)

1 TJU - Tianjin University
2 Harvard University
3 ISM2 - Institut des Sciences Moléculaires de Marseille

Palladium-catalyzed intramolecular arylation provides bowl-shaped azaindenocorannulenes 7−9. Crystals of 8 show bowl-in-bowl columnar stacking. A substituent model rationalizes the first reduction potential of 18 related molecular bowls. The absolute configurations of bowls 7 and 9 are correlated with VCD and ECD spectra. The bowl inversion barrier of 9 (>190 kJ/mol) shows it to be more inert configurationally than chiral biaryl, phosphenes, or [n]helicenes.

Domaines: Chimie organique; Catalyse

Xiaoqi Tian, Loïc M Roch, Nicolas Vanthuyne, Jun Xu, Kim K Baldridge, et al.. Azaindenocorannulenes: Synthesis, Properties, and Chirality. Organic Letters, 2019, 21 (10), pp.3510-3513. ⟨10.1021/acs.orglett.9b00718⟩. ⟨hal-02514517⟩