A rapid and versatile method for the preparation of planar chiral [2.2]paracyclophane-derived pyridines and pyridine N-oxides is reported. The potential utility of these compounds in Lewis base catalysis is briefly introduced.

Two planar chiral heteroaryl monophosphines have been synthesised and studied. The phosphines are readily prepared from 4-imidazole[2.2]paracyclophane by selective deprotonation and reaction with the appropriate dialkylchlorophosphines. The planar chiral imidazole was constructed in four steps from readily available [2.2]paracyclophane. The 2-phosphino-N-[2.2]paracyclophanes were active in the Suzuki-Miyaura coupling of aryl bromides and chlorides. Coordination studies indicate P,N-chelation in the solid-state. These studies lay the foundations for asymmetric couplings.

In this communication we report the short synthesis of a variety of planar chiral triazole‐based phosphanes. These molecules have been readily prepared from 4‐azido[2.2]paracyclophane in two steps. It was observed that the stability of the resulting phosphanes was dependent on the C‐4 substituent. The efficacy of the new phosphanes in the palladium‐mediated Suzuki–Miyaura coupling reaction was evaluated. The phosphanes proved to be more effective than previously prepared planar chiral [2.2]paracyclophane‐based phosphanes.

An enantiomerically pure planar chiral pyridine-based palladacycle was prepared from [2.2]paracyclophane in just four steps. The palladacycle shows potential in catalysis, mediating the Suzuki coupling of an aryl chloride. It also permits the ortho bromination of [2.2]paracyclophane, a reaction that can be hard to achieve selectively.

Planar Chiral Triazole-Based Phosphanes Derived from [2.2]Paracyclophane and Their Activity in Suzuki Coupling Reactions. -Four cyclophane derivatives with triazole-phosphane moieties are synthesized and tested as ligands in Suzuki cross--coupling reactions with compound (V) giving the best results. -(GLOVER, J. E.; MARTIN, D. J.; PLIEGER, P. G.; ROWLANDS*, G. J.; Eur. J. Org. Chem. 2013, 9, 1671-1675, http://dx.doi.org/10.1002/ejoc.201201601 ; Inst. Fundam. Sci., Massey Univ., Palmerston North, N. Z.; Eng.) -Roessler 32-094