A planar chiral non-metallocenic analogue of the most popular N,N-dimethylbenzylaminate palladacycle

Unprecedented pseudo-ortho and ortho metallation of [2.2]paracyclophanes – a methyl group matters

“…A second directing group which we tested during our studies was the N,N-dimethylaminomethyl moiety. As previously reported by three different groups, [24][25][26] this moiety is very suitable for palladium-catalyzed C-H bond activation of [2.2]paracyclophanes, especially in ortho position. Therefore, using this directing group and the reaction conditions described above, we expected a highly selective ortho metallation to occur.…”

Regioselective ortho‐Palladation of [2.2]Paracyclophane Scaffolds: Accessing Planar and Central Chiral N,C‐Palladacycles

“…The ortho ‐palladated N,C‐dimer 3 a using 2 a (previously established by Dunina and co‐workers) as well as its transformation into the monometallic derivative 4 a were performed under our modified reaction conditions (Scheme 1). [15] …”

“…The ortho-palladated N,C-dimer 3 a using 2 a (previously established by Dunina and co-workers) as well as its transformation into the monometallic derivative 4 a were performed under our modified reaction conditions (Scheme 1). [15] Combining two or more chiral elements into a ligand or catalyst system could enable stereochemical cooperativity, which provides a powerful strategy for the optimization and tuning of the stereochemical outcome. Therefore we incorporated an additional central-chiral element into the PCP scaffold which exhibits the innate element of planar chirality.…”