Intermolecular hydroaminoalkylation reactions of alkynes with secondary amines, which selectively give access to allylic amines with E configuration of the alkene unit, are achieved in the presence of titanium catalysts. Successful reactions of symmetrically substituted diaryl‐ and dialkylalkynes as well as a terminal alkyne take place with N‐benzylanilines, N‐alkylanilines, and N‐alkylbenzylamines.

Intermolecular hydroaminoalkylation reactions of 1,1-and 1,3disubstituted allenes as well as methylenecyclopropanes with secondary amines can be achieved in the presence of a 2,6bis(phenylamino)pyridinato titanium catalyst at 140 °C within 2-8 h. Corresponding reactions of allenes with N-benzylanilines deliver branched allylamine products in very good yields (up to 83 %) and with branched-linear-ratios between 75 : 25 and 95 : 5.In contrast, bicyclic methylenecyclopropanes undergo hydroaminoalkylation with N-benzylanilines or N-alkylbenzylamines to give linear products in good to excellent yields (up to 98 %) with perfect regio-and diastereoselectivity. The corresponding 1,2,3-trisubstituted (2-aminoethyl)cyclopropane products exhibit a structurally interesting cis-orientation of all three cyclopropane hydrogen atoms.

The benzene ligand at CpV(η 6 À C 6 H 6 ) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2 a and 2 b) and benzofulvene complexes (3 a and 3 b). The molecular structures of the target compounds suggest a π-η 5 :σ-η 1 coordination mode with a vanadium III center. With the sterically low demanding 6,6-dimethylpentafulvene, a CÀ H activation at the leaving ligand is observed, yielding the ring-substituted vanadocene II 4. The reactivity of the pentafulvene complexes was investigated. A series of unprecedented vanadocene III compounds were synthesized: Under mild conditions, EÀ H splitting of 4tert-butylphenol, diphenylamine, and 2,6-diisopropylaniline yield well characterized examples of rare vanadocene III phenolate and amide complexes. Insertion reactions into the VÀ C exo bond of the pentafulvene complexes by multiple bond containing substrates were found for acetone, 4-chlorobenzonitril and N,N'-dicyclohexylcarbodiimide.

Hydroaminoalkylation! In this work, the conversion of alkynes into allylic amines within an unbelievably short reaction time of 4 h is presented. In addition to the fast reaction, hydroaminoalkylation is promoted by broad scope, high yields, and excellent stereoselectivity to provide access to synthetically useful products in record time. More information can be found in the Communication by R. Beckhaus, S. Doye, et al. on page 6899.

The Cover Feature illustrates the titanium‐catalyzed α‐functionalization of secondary amines with either allenes or methylenecyclopropanes. To achieve this, the employed catalyst must act like a wizard, miraculously activating C−H bonds and thereby combining the starting materials regio‐ and stereoselectively. Cover design by Melissa Schlüschen. More information can be found in the Research Article by S. Doye et al.