The Multifaceted Chemistry of [2.2]Paracyclophane‐Based Thioethers with Palladium(II) Complexes

Abstract

AbstractThe reactions of planar chiral ([2.2]paracyclophan‐4‐yl)methyl thioethers ([2.2]PCP‐CH2‐SR) with various palladium(II) sources (PdL2) were studied. Unexpectedly, with most of the sulfur substrates investigated (SR=Ph, 2‐pyridyl, Me, n‐dodecyl), and independently of the PdL2 salt employed (L=TFA, OAc, OPiv, Cl, Br), loss of the SR sulfanyl unit, along with incorporation of one palladium L ligand to the lateral benzylic position of the [2.2]PCP core, has been observed. In contrast, the precursor featuring a t‐butylsulfanyl group (R=t‐Bu) exhibited a distinct reactivity. An ortho C(sp2)−H activation took place, and allowed the formation of a [2.2]paracyclophane‐based SC‐palladacycle, in an efficient and highly diastereoselective manner (83 % yield, single diastereoisomer).