Introduction and Preface

Computational insights into the synergistic interplay of ligand and fluorine effects in palladium-catalyzed regiodivergent decarboxylative allylic alkylation

“…The advancement of efficient and atom-economic methods for constructing C–C and C–X bonds is a cornerstone in organic chemistry, which enables the synthesis of complex molecular structures with diverse functionalities. 1,2 In this respect, the transition metal-catalyzed decarboxylative allylic alkylation of allyl enol carbonates and allyl β-ketoesters, pioneered by the independent works of Saegusa and Tsuji, 3 has garnered considerable attention. 2 These reactions demonstrate a remarkable capability of generating both nucleophilic and electrophilic species in situ , with the exclusive byproduct being carbon dioxide.…”

Sustainable Manganese‐Catalyzed C−H Activation/Hydroarylation of Imines

“…[10] In sharp contrast, less expensive and less toxic manganese has only recently been identified as catalyst for the position-selective C = Heth ydroarylations. [11] Despite this indisputable progress, the manganese catalysis regime required drastic conditions with Et 2 Oa st he solventa tareaction temperature of 100 8C, thus calling for high-pressure technologiesa nd special safety features.H owever,w ithin our program on sustainable catalysis, [12] we have now devised most user-friendlym anga-nese-catalyzed site-selective CÀHa ctivation/hydroarylations [13] of iminesw ith ample substrates cope. Notable features of our findings include i) general assembly of bioactive aminomethylated indoles, key motifs in naturalp roducts and pharmaceuticals, [14] ii)a mostu ser-friendly reaction mediumf or site-selective CÀHf unctionalizations at ambient pressure, iii)synthetically useful removable [15] pyri(mi)dyl groups, and iv) detailed mechanistic insights into the working mode of the manganese-catalyzed CÀHa ctivation (Scheme 1).…”