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

A selective palladation: Planar and central chiral cyclophanyl-derived mono- and binuclear N,C-palladacycles are prepared by regioselective ortho-palladation of amine- and imine-functionalized [2.2]paracyclophanes employing stepwise Pd(OAc)$_{2}$ and LiCl followed by modular treatment with PPh$_{3}$, PCy$_{3}$ and (Ph$_{2}$PCH$_{2}$)$_{2}$. The regioselective ortho-palladation mono- and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single-crystal X-ray analysis. In this report, we describe a series of cyclophanyl-derived mono- and binuclear N,C-palladacycles by regioselective ortho-palladation of amine-functionalized [2.2]paracyclophanes. Employing Pd(OAc)$_{2}$ followed by LiCl and with the subsequent modular treatment of Ph$_{3}$P, Cy$_{3}$P, and (Ph$_{2}$PCH$_{2}$)$_{2}$, this strategy allows to prepare stable cyclophanyl-derived planar and central chiral N,C-palladacycles in a highly selective manner. The regioselective ortho-palladation mono- and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single-crystal X-ray analysis

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

In this report, we describe a series of cyclophanyl-derived mono- and binuclear N,C-palladacycles by regioselective ortho-palladation of amine-functionalized [2.2]paracyclophanes. Employing Pd(OAc)(2) followed by LiCl and with the subsequent modular treatment of Ph3P, Cy3P, and (Ph2PCH2)(2), this strategy allows to prepare stable cyclophanyl-derived planar and central chiral N,C-palladacycles in a highly selective manner. The regioselective ortho-palladation mono- and bimetallic product formation was analyzed by detailed spectroscopic techniques, mass spectrometry and unambiguously confirmed by single-crystal X-ray analysis.Peer reviewe

Kinetics and Mechanism of the Palladium-Catalyzed Oxidative Arylating Carbocyclization of Allenynes

Pd-catalyzed C–C bond-forming reactions under oxidative conditions constitute a class of important and widely used synthetic protocols. This Article describes a mechanistic investigation of the arylating carbocyclization of allenynes using boronic acids and focuses on the correlation between reaction conditions and product selectivity. Isotope effects confirm that either allenic or propargylic C–H activation occurs directly after substrate binding. With an excess of H₂O, a triene product is selectively formed via allenic C–H activation. The latter C–H activation was found to be turnover-limiting and the reaction zeroth order in reactants as well as the oxidant. A dominant feature is continuous catalyst activation, which was shown to occur even in the absence of substrate. Smaller amounts of H₂O lead to mixtures of triene and vinylallene products, where the latter is formed via propargylic C–H activation. The formation of triene occurs only in the presence of ArB­(OH)₂. Vinylallene, on the other hand, was shown to be formed by consumption of (ArBO)₃ as a first-order reactant. Conditions with sub-stoichiometric BF₃·OEt₂ gave selectively the vinylallene product, and the reaction is first order in PhB­(OH)₂. Both C–H activation and transmetalation influence the reaction rate. However, with electron-deficient ArB­(OH)₂, C–H activation is turnover-limiting. It was difficult to establish the order of transmetalation vs C–H activation with certainty, but the results suggest that BF₃·OEt₂ promotes an early transmetalation. The catalytically active species were found to be dependent on the reaction conditions, and H₂O is a crucial parameter in the control of selectivity