Synfacts 2008(3): 0302-0302  
DOI: 10.1055/s-2008-1042736
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

Direct Aminoalkylation via Nickel-Catalyzed Negishi Cross-Coupling Reactions

Contributor(s):Paul Knochel, Tobias Thaler
L. Melzig, A. Gavryushin, P. Knochel*
Ludwig-Maximilians-Universität München, Germany
Direct Aminoalkylation of Arenes and Hetarenes via Ni-Catalyzed Negishi Cross-Coupling Reactions
Org. Lett.  2007,  9:  5529-5532  
Further Information

Publication History

Publication Date:
21 February 2008 (online)


Significance

A new general method for the one-pot introduction of aminoalkyl groups via Negishi-type cross-coupling is reported. It was applied to the cross-coupling with both aryl and hetaryl halides and triflates furnishing the respective products with good to excellent yields. It is noteworthy that cross-coupling of tropanyl zinc reagents proceeds with 100% exo-selectivity. This is due to the stereospecific formation of the corresponding Grignard reagent.

Comment

Molander described the first direct coupling of potassium aminoalkyltrifluoroborates with aryl and hetaryl halides (Org. Lett. 2007, 9, 203; Org. Lett. 2007, 9, 1597). So far, however, no other cross-coupling reaction of an aminoalkyl organometallic species possessing a basic nitrogen has been reported. In this article the first Negishi-type cross-coupling between aminoalkyl­zinc reagents and aryl, hetaryl halides and triflates is presented. The easy accessibility of the amino­alkylzinc reagents via magnesium insertion and transmetallation and the frequent occurrence of aminoalkyl moieties in biologically active materials make this method a promising tool for the development of new drug libraries.