General methods to prepare chiral pyridine derivatives are greatly sought after due to their significance in medicinal chemistry. Here, we report highly enantioselective catalytic transformations of poorly reactive β-substituted alkenyl pyridines to access a wide range of alkylated chiral pyridines. The simple methodology involves reactivity enhancement via Lewis acid (LA) activation, the use of readily available and highly reactive Grignard reagents, and a copper-chiral diphosphine ligand catalyst. Apart from allowing the introduction of different linear, branched, cyclic, and functionalised alkyl chains at the β-position of alkenyl pyridines, the catalytic system also shows high functional group tolerance.
Catalytic enantioselective addition of organometallic nucleophiles to ketones is among the most straightforward approaches to the synthesis of chiral tertiary alcohols. The first such catalytic methodologies using the highly reactive organomagnesium reagents, which are the preferred organometallic reagents in terms of cost, availability, atom efficiency, and structural diversity, were developed only during the last five years. This Concept article highlights the fundamental breakthrough that made the development of methodologies for highly enantioselective Cu(I) -catalyzed alkylation of ketones using organomagnesium reagents possible.
To celebrate International Women′s Day on March 8th 2016, Chemistry – A European Journal is publishing a special issue dedicated to women around the world currently working in chemical research. The cover picture shows the frontispieces of the Concept, Review, and Minireview articles published in this issue, highlighting the broad range of chemistry that is currently being carried out by female researchers. In the top row from left to right: S. Harutyunyan et al. (page 3558 ff.), J. Sponer et al. (page 3572 ff.), and M. Brimble et al. (page 3622 ff.). In the middle row from left to right: M. Resmini et al. (page 3612 ff.), the logo for International Women′s Day 2016 (http://www. internationalwomensday.com/), and Y. Xie and J. Xie (page 3588 ff.). In the bottom row from left to right: I. Beletskaya and P. Sazonov (page 3644 ff.), T. Gaich and M. Pfaffenbach (page 3600 ff.), and A. Lattanzi and S. Meninno (page 3632 ff.).
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