RESUMEN
Herein, we disclose an eco-efficient redox-neutral iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light (427 nm) giving cyclic hydrazine derivatives with dr ranging from 82 : 18 to >96 : 4. This earth-abundant metal promoted sequence proceeds efficiently under ligand-free conditions based on a LMCT process and opens a route to new chiral heterocycles.
RESUMEN
A domino Vinylogous aza-Michael-Aldol-Cyclocondensation (aza-VMAC) reaction was achieved with a series of alkylidene Meldrum's acid derivatives under simple operational conditions paving the way to novel pyrano[2,3-c]pyrroles in an excellent diasteroselectivity (>96 : 4), encompassing the relative control of three contiguous stereocenters.
RESUMEN
A highly diastereoselective organocatalyzed domino vinylogous sulfa-Michael-aldol-cyclocondensation (VMAC) reaction has been developed using alkylidene Meldrum's acid as dienes highlighting two vinylogous steps, an unprecedented sulfa-1,6-conjugate addition and a diastereoselective aldol reaction triggering a formal (4+2) cycloaddition. This work opens a new route towards bio-relevant and original tricyclic thiochroman derivatives.
RESUMEN
From achiral imidazolinium salts, chiral transition metal complexes containing an N-heterocyclic carbene (NHC) ligand were prepared (metal = palladium, copper, silver, gold, rhodium). Axial chirality in these complexes results from the formation of the metal-carbene bond leading to the restriction of rotation of dissymmetric N-aryl substituents about the C-N bond. When these complexes exhibited a sufficient configurational stability, a resolution by chiral high-performance liquid chromatography (HPLC) on preparative scale enabled isolation of enantiomers with excellent enantiopurities (>99% ee) and good yields. A study of the enantiomerization barriers revealed the effect of the backbone nature as well as the type of transition metal on its values. Nevertheless, the evaluation of palladium-based complexes in asymmetric intramolecular α-arylation of amides demonstrated that the ability to induce an enantioselectivity cannot be correlated to the configurational stability of the precatalysts.
Asunto(s)
Complejos de Coordinación , Catálisis , Ligandos , Metano/análogos & derivados , EstereoisomerismoRESUMEN
The controlled preparation of chiral emissive transition metal complexes is fundamental in the field of circularly polarized luminescence (CPL) active molecular materials. For this purpose, enantiopure Zn(ii) complexes 1 and 2 based on a tetradentate salen ligand surrounded by [4]helicene moieties, together with their racemic counterpart 3, have been herein synthesized. Chirality is primarily brought about by chiral 1,2-cyclohexane-diamines. Alternatively, achiral complex 4 based on ortho-phenylene-diamine has been prepared as well. Single crystal X-ray diffraction analyses have been performed on helicenic intermediates 8 and 9 and complexes 1 and 4. Complexes 1 and 4 display the typical tetradentate O,N,N,O coordination around Zn(ii) characteristic of salen ligands, and bear two [4]helicene moieties. The zinc complexes are luminescent in the visible range around 560 nm at room temperature in aerated solutions with the QY reaching ca. 15% for a luminescence lifetime of 5.5 ns. The optical activities of these complexes have been assessed by CD and CPL, and compared to DFT calculations.