Synthesis of Optically Active Aromatic Ether Ketone Macrocycles Containing 2,2′-Dimethoxy-1,1′-binaphthyl-6,6′-diyl Moieties

Abstract

Optically active aromatic ether ketone macrocycles containing 2,2′-dimethoxy-1,1′-binaphthyl-6,6′-diyl moieties were synthesized through electrophilic aromatic substitution reaction and stepwise nucleophilic aromatic substitution reactions. Structures of the resulting macrocycles were confirmed by NMR and matrix assisted laser desorption/ionization time of flight (MALDI-TOF) mass measurements.

Keywords:

• Binaphthyl
• optically active macrocycles
• oxybiphenol
• two-step nucleophilic aromatic substitution reaction

ACKNOWLEDGMENT

This work was supported by a Grant-in-Aid for Young Scientists (B) (No. 20750173) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan.

Notes

^a Reaction procedure: A DMF solution (12 mL) of diol 4a–c (0.5 mmol) was added dropwise over 6 h to a DMF solution (1.5 mL) of binaphthyl 3 (3 mmol) in the presence of K₂CO₃ (1.5 mmol) in N₂ atmosphere. The reaction mixture was further stirred at 150°C for 24 h.

^b Isolated yield.

^a Reaction conditions: Binaphthyl 5a–c, 0.1 mmol; diol 4a–c, 0.1 mmol; K₂CO₃, 0.3 mmol; 150°C; N₂ atmosphere.

^a Measured in CHCl₃ (5.0 × 10⁻⁵ mol/L).