The C-C bond forming catalytic hydroaminoalkylation of terminal alkenes, 1,3-dienes, or styrenes allows a direct and highly atom efficient (100 %) synthesis of amines which can result in the formation of two regioisomers, the linear and the branched product. We present a new titanium catalyst with 2,6-bis(phenylamino)pyridinato ligands for intermolecular hydroaminoalkylation reactions of styrenes and 1-phenyl-1,3-butadienes that delivers the corresponding linear hydroaminoalkylation products with excellent regioselectivities.

An easily accessible formamidinate ligand-bearing titanium complex initially synthesized by Eisen et al. is used as catalyst for intermolecular hydroaminoalkylation reactions of unactivated, sterically demanding 1,1- and 1,2-disubstituted alkenes and styrenes with secondary amines. The corresponding reactions, which have never been achieved with titanium catalysts before, take place with excellent regioselectivity (up to 99 : 1) and in addition, corresponding reactions of 1,3-butadienes with N-methylbenzylamine are also described for the first time.

Ti me kangaroo down: Conjugated dienes undergo intermolecular hydroaminoalkylation in the presence of Ti catalyst [Ind2 TiMe2 ] (Ind=η(5) -indenyl). This new reaction offers a highly atom-efficient approach to homoallylic amines from 1,3-butadienes.

Die über eine C‐C‐Bindungsknüpfung verlaufende katalytische Hydroaminoalkylierung von terminalen Alkenen, 1,3‐Dienen und Styrolen ermöglicht eine direkte und zu 100 % atomökonomische Synthese von Aminen, bei der zwei Regioisomere (linear und verzweigt) gebildet werden können. Hier berichten wir über einen neuen Titan‐Katalysator mit 2,6‐Bis(phenylamino)pyridinato‐Liganden, in dessen Gegenwart die intermolekulare Hydroaminoalkylierung von Styrolen und 1‐Phenyl‐1,3‐butadienen mit exzellenten Regioselektivitäten zugunsten des linearen Produktes erreicht werden kann.

Abstract.A simple, reliable, and reproducible procedure for the multigram synthesis of highly pure bis(indenyl)dimethyltitanium is presented. The procedure relies on a one-pot conversion of inexpensive indene, methyllithium, and titanium tetrachloride to [Ind 2 TiMe 2 ] and