Structural diversity in alkali metal and alkali metal magnesiate chemistry of the bulky 2,6-diisopropyl-N-(trimethylsilyl)anilino ligand

Bulky amido ligands are precious in s-block chemistry since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky aryl-silyl amido ligand [N(SiMe3)(Dipp)] (Dipp = 2,6-iPr2-C6H3). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by PMDETA or TMEDA gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure but TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3)(Dipp)}2(μ-nBu)]∞ (M = Na or K), are also revealed though these breakdown to their homometallic components in donor solvent as revealed through NMR and DOSY studies

Visible-light excitation of iminium ions enables the enantioselective catalytic ?-alkylation of enals

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved. Chiral iminium ions - generated upon condensation of α,β-unsaturated aldehydes and amine catalysts - are used extensively by chemists to make chiral molecules in enantioenriched form. In contrast, their potential to absorb light and promote stereocontrolled photochemical processes remains unexplored. This is despite the fact that visible-light absorption by iminium ions is a naturally occurring event that triggers the mechanism of vision in higher organisms. Herein we demonstrate that the direct excitation of chiral iminium ions can unlock unconventional reaction pathways, enabling enantioselective catalytic photochemical β-alkylations of enals that cannot be realized via thermal activation. The chemistry uses readily available alkyl silanes, which are recalcitrant to classical conjugate additions, and occurs under illumination by visible-light-emitting diodes. Crucial to success was the design of a chiral amine catalyst with well-tailored electronic properties that can generate a photo-active iminium ion while providing the source of stereochemical induction. This strategy is expected to offer new opportunities for reaction design in the field of enantioselective catalytic photochemistry