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Oxygen is a molecule of utmost importance in our lives. Beside its vital role for the respiration and sustaining of organisms, oxygen is involved in numerous chemical and physical processes. Upon combination of the different forms of molecular oxygen species with various activation modes, substrates, and reaction conditions an extremely wide chemical space can be covered that enables rich applications of diverse oxygenation processes. This Review provides an instructive overview of the individual properties and reactivities of oxygen species and illustrates their importance in nature, everyday life, and in the context of chemical synthesis.

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A combined spectroscopic, synthetic, and apparative study has allowed a more detailed mechanistic rationalization of several recently reported eosin Y-catalyzed aromatic substitutions at arenediazonium salts. The operation of rapid acid-base equilibria, direct photolysis pathways, and radical chain reactions has been discussed on the basis of pH, solvent polarity, lamp type, absorption properties, and quantum yields. Determination of the latter proved to be an especially valuable tool for the distinction between radical chain and photocatalytic reactions.

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Photo-sensitized synthesis of arylsulfides from arenediazonium salts in the presence of eosin Y has been developed. This protocol exhibits high functional group tolerance and a wide substrate scope and is an attractive alternative to the thermal reaction that involves explosive intermediates.

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The development of a general and practical zinc-catalyzed enantioselective alkyne addition methodology is reported. The commercially available ProPhenol ligand (1) has facilitated the addition of a wide range of zinc alkynylides to aryl, aliphatic, and α,ß-unsaturated aldehydes in high yield and enantioselectivity. New insights into the mechanism of this reaction have resulted in a significant reduction in reagent stoichiometry, enabling the use of precious alkynes and avoiding the use of excess dimethylzinc. The enantioenriched propargylic alcohols from this reaction serve as versatile synthetic intermediates and have enabled efficient syntheses of several complex natural products.

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This tutorial review is intended to provide the reader with a timely review of major developments and the current state-of-the-art of palladium-catalyzed cross-coupling reactions with Grignard reagents. Organomagnesium reagents, the most reactive and most easily accessible nucleophiles for carbon-carbon bond forming cross-coupling reactions, were the first nucleophiles ever employed in cross-coupling reactions, but have only recently been re-discovered for highly efficient and (stereo)selective coupling reactions. This is mostly a consequence of improved catalyst systems with bulky phosphine, phosphonate or carbene ligands and new metal-halogen exchange procedures for the generation of functionalized Grignard reagents.

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A series of novel 2-alkylidene imidazolines has been synthesized from imidazolium halides and substituted alkyl halides in the presence of base. The resultant exocyclic enediamines have been characterized and their nucleophilicity has been evaluated upon NMR spectroscopic data and substitution reactions.

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Iron-catalyzed cross-coupling reactions have, over the past years, developed to maturity and today are an integral part of the organic chemist's toolkit. They benefit from low costs, operational simplicity, and high reactivity and thus constitute the "green" sister of the palladium and nickel establishment. This timely Review traces back major achievements, discusses their mechanistic background, and highlights numerous applications to molecular synthesis.Iron-catalyzed carbon-carbon bond-forming reactions have matured to an indispensable class of reactions in organic synthesis. The advent of economically and ecologically attractive iron catalysts in the past years has stepped up the competition with the established palladium and nickel catalyst systems that have dominated the field for more than 30 years, but suffer from high costs, toxicity, and sometimes low reactivity. Iron-catalyzed protocols do not merely benefit from economic advantages but entertain a rich manifold of reactivity patterns and tolerate various functional groups. The past years have witnessed a rapid development with ever-more-efficient protocols for the cross-coupling between alkyl, alkenyl, alkynyl, aryl, and acyl moieties becoming available to organic chemists. This Review intends to shed light onto the versatility that iron-catalyzed cross-coupling reactions offer, summarize major achievements, and clear the way for further use of such superior methodologies in the synthesis of fine chemicals, bioactive molecules, and materials.

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Our recent development of a proline-derived bimetallic catalyst has led to a number of efficient, catalytic, enantioselective transformations. Herein, we report a practical and general alkynylation of aromatic and alpha,beta-unsaturated aldehydes using our zinc catalyst system.

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The acid-catalyzed condensation of aldehydes and acetamide has been shown to provide a pool of diverse equilibrating species. For the first time, the synthesis of substituted 1-N-acylamino-1,3-butadienes has been accomplished directly in moderate yields upon telomerization of two molecules of aldehyde with one molecule of carboxamide. Detailed spectroscopic and computational investigations establish the favourable formation of all-trans aminodienes under the reaction conditions. Employment thereof as diene building blocks in Diels-Alder reactions allows for the synthesis of carbocyclic molecules with high stereocontrol.

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The acid-catalyzed condensation chemistry of simple amides and aldehydes provides a highly prolific source of diverse reactants for irreversible follow-up reactions. Amide-aldehyde mixtures have been successfully employed in multicomponent syntheses of N-acyl alpha-amino acids (via palladium-catalyzed amidocarbonylation) and various cyclohexene, cyclohexadiene, and benzene derivatives (via the amide-aldehyde-dienophile (AAD) reaction).