Anthony Chartoire

[Pd(IPr*)(cinnamyl)Cl]: An Efficient Pre‐catalyst for the Preparation of Tetra‐ortho‐substituted Biaryls by Suzuki–Miyaura Cross‐Coupling

The bigger the better: The new well-defined [Pd(IPr*)(cin)Cl] pre-catalyst is described. This complex proves to be highly active in the Suzuki-Miyaura cross-coupling for the synthesis of tetra-ortho-substituted biaryls under mild conditions. IPr* is reported as the largest N-heterocyclic carbene (NHC) to date for [Pd(NHC)(cin)Cl] complexes, explaining the high reactivity observed for this complex in this challenging transformation.

Extending the utility of [Pd(NHC)(cinnamyl)Cl] precatalysts: Direct arylation of heterocycles

Summary The use of [Pd(NHC)(cinnamyl)Cl] precatalysts in the direct arylation of heterocycles has been investigated. Among four different precatalysts, [Pd(SIPr)(cinnamyl)Cl] proved to be the most efficient promoter of the reaction. The C–H functionalization of sulfur- or nitrogen-containing heterocycles has been achieved at low catalyst loadings. These catalyst charges range from 0.1 to 0.01 mol % palladium.

Arylation of amines in alkane solvents by using well-defined palladium-N-heterocyclic carbene complexes

The use of the ITent‐based series of Pd‐N‐heterocyclic carbenes precatalysts (Tent= Tentacular) enables the Buchwald–Hartwig amine arylation reaction in apolar alkane solvents. The use of such solvents is rare because of their poor solvation properties. Nonetheless, they could be of interest for industrial applications, as they can be disposed of in an energetically favorable manner and may potentially simplify product isolation. The excellent solubility of the precatalysts permitted the desired products to be obtained in yields ranging from 75 to 96 %, even with deactivated and functionalized coupling partners.

CHAPTER 4:Advances in C–C and C–X Coupling Using Palladium–N-Heterocyclic Carbene (Pd–NHC) Complexes

This chapter presents an overview of developments using Pd–NHC systems in cross-coupling catalysis. The reactions examined are the major Pd-mediated transformations including those discovered by the 2010 Nobel Prize in Chemistry winners.