Cp*Co -catalyzed highly regioselective mono- and bis-annulation of arylamides with 1,3-diynes using N-OMe as an internal oxidant is demonstrated. This atom-economical transformation does not require any external oxidant and tolerates many functional groups. Various symmetrical and unsymmetrical heterocycles (homo and hetero) are accessed with predictable regio- and chemoselectivity.

The use of unbiased aliphatic alkene as the coupling partner for C−H olefination continues to be a challenging task. A suitable chelating directing group allowed ortho C−H olefination of benzyl phosphonamide with unactivated aliphatic alkenes. The broad substrate scope with respect to variation of benzyl phosphonamides and aliphatic alkenes as well as examples of sequential hetero-bis-olefinations offer diversity along with excellent linear/branch selectivity.

The C–H indolation of heteroarenes was realized using the benziodoxolone hypervalent iodine reagents indoleBXs. Functionalization of the C–H bond in bipyridinones and quinoline N-oxides catalyzed by a rhodium complex allowed to incorporate indole rings into aza-heteroaromatic compounds. These new transformations displayed complete regioselectivity for the C-6 position of bipyridinones and the C-8 position of quinoline N-oxides and tolerated a broad range of functionalities, such as halogens, ethers, or trifluoromethyl groups.

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A Pd-catalyzed method based on the use of a molecular tether is described for olefin difunctionalization. Enabled by an easily introduced trifluoroacetaldehyde-derived tether, a simultaneous introduction of oxygen and nitrogen heteroatoms across unsaturated carbon–carbon bonds was achieved under oxidative conditions, most probably via high-valent Pd intermediates. Good yields and high diastereoselectivity were obtained with aryl-substituted alkenes, whereas nonterminal alkyl-substituted olefins gave aza-Heck products. Tether cleavage under mild conditions provided fast access to functionalized β-amino alcohols.

Bei der Umsetzung von Dithiocarbamaten (II) mit Phenacylbromid (III) werden entweder phenacylsubstituierte Dithiocarbamate (IV) oder, wenn bei der Herstellung des Dithiocarbamats von primären Aminen ausgegangen wird, Thiazolin‐2‐thione (V) erhalten.

We report an enantioselective palladium-catalyzed trans -hydroalkoxylation of propargylic amines with a trifluoroacetaldehyde-derived tether to build chiral oxazolidines. Diastereoselective hydrogenation using a heterogeneous palladium catalyst then gave access to protected benzylic amino alcohols in 45–87% yields and 84–94% ee values. Hydroalkoxylation of the alkynes required a catalytic amount of aryl iodide, highlighting the counterintuitive key role played by a putative Pd(II)/ArI oxidative addition complex to promote oxypalladation/protodemetalation.

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