This paper describes the synthesis and characterization of 21 chiral monodentate ligands L, assembled of three building blocks utilizing amide bonds: a metal binding triphenylphosphine, a chiral cyclic diamine and an additional substituent for fine‐tuning the steric and/or electronic properties. Cis square‐planar metal complexes of RhI and PtII with ML2 stoichiometry have been prepared and characterized by spectroscopic methods (NMR, IR, UV‐Vis, CD) and DFT calculations. A key feature of the metal complexes is a prochiral metal coordination sphere and “backdoor induction” of chirality from a distant chiral source via an outer‐coordination sphere, well‐defined by aromatic stacking and hydrogen‐bonding. The rhodium complexes were used as catalysts in asymmetric hydrogenation of α,β‐dehydroamino acids with excellent yield and selectivity (up to 97 % ee), strongly supporting the “backdoor induction” hypothesis.
We present a double-stranded ferrocene pseudopeptide 2b which exhibits stimuli responsive chirality inversion triggered by solvent exchange or acid addition. Compound 2b exists as a mixture of self-assembled fast exchanging...
New anion receptor N 1 ,N 8 -bis[1H-pyrro-2-yl-methylidene]-3,6-dichloro-9H-carbazole-1,8-diamine (3) was synthesized and its binding properties towards anions (Cl -, Br -, AcO -and H2PO4 -) investigated by UV/Vis spectroscopy. In order to find the most stable structure of receptor 3, geometries of all possible isomers of 3 were optimized by the DFT/B3LYP method. It has been determined that receptor 3 forms complexes with a 1:1 stoichiometry with all the studied anions and no significant selectivity with respect to anion geometry was found. However, 1,8-dipyrrolecarbazole Schiff-base 3 binds oxoanions (H2PO4 -and AcO -) more strongly than spherical halogenide (Cl -and Br -) anions.
Amides are common molecules which are most often prepared using benzotriazole oxide coupling reagents. Such amides can be derivatised with compounds that contain a triple carbon-carbon bond in order to...
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