Published in The Journal of organic chemistry
The mechanism of the asymmetric BINOL-derived hydroxyl carboxylic acid catalyzed allylboration of benzaldehyde was investigated using density functional theory calculations. A new reaction model is proposed, and the roles of the two Brønsted acidic sites of the catalyst elucidated. Catalyst distortion was found to be a key factor in determining ste...
Published in The Journal of organic chemistry
It was found by us that the P-C coupling reaction of >P(O)H reagents with PhX (X = I and Br) in the presence of NiCl2/Zn as the precursors for the assumed Ni(0) complexant together with 2,2'-bipyridine as the ligand took place only with PhI at 50/70 °C. M06-2X/6-31G(d,p)//PCM(MeCN) calculations for the reaction of Ph2P(O)H and PhX revealed a favora...
Published in The Journal of Organic Chemistry
Togni’s benziodoxole-based reagents are widely used in trifluoromethylation reactions. It has been established that the kinetically stable hypervalent iodine form (I–CF3) of the reagents is thermodynamically less stable than its acyclic ether isomer (O–CF3). On the other hand, the trifluoromethylthio analogue exists in the thermodynamically stable ...
Published in The Journal of Organic Chemistry
The development of a multifunctional catalyst, which mimics the promiscuity of enzymes, that would catalyze more than one chemical transformation in a single reaction vessel is one of the key points of modern sustainable chemistry. The results of our experiments indicated that Grubbs-type catalysts possess such multitask activity, catalyzing the tr...
Published in The Journal of organic chemistry
We have quantum chemically analyzed the competition between the bimolecular nucleophilic substitution (SN2) and base-induced elimination (E2) pathways for F- + CH3CH2Cl and PH2- + CH3CH2Cl using the activation strain model and Kohn-Sham molecular orbital theory at ZORA-OLYP/QZ4P. Herein, we correct an earlier study that intuitively attributed the m...
Published in The Journal of Organic Chemistry
The chemistry of strained unsaturated cyclic compounds has experienced remarkable growth in recent years via the development of metal–free click reactions. Among these reactions, the cycloaddition of cyclopropenes and their analogues to ortho -quinones has been established as a highly promising click reaction. The present work investigates the mech...
A BF3×OEt2 catalyzed intramolecular Povarov reaction was used to synthesize a library of 15 chromenopyridine fused thiazolino-2-pyridone peptidomimetics. The reaction works with a range of O-alkylated salicylaldehydes and amino functionalized thiazolino-2-pyridones, to generate polyheterocycles with diverse substitution. The synthesized compounds w...
Published in The Journal of organic chemistry
The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired co...
Published in The Journal of organic chemistry
Enantiopure aziridin-2-yl methanols 3-7 are used as highly effective sensors for enantiodiscrimination of α-racemic carboxylic acids containing tertiary or quaternary stereogenic centers. A linear correlation between theoretical and observed % ee values for CSA-3 and enantiomerically enriched samples of mandelic acid has been observed, indicating t...
Published in The Journal of Organic Chemistry
The synthesis of shape-persistent organic cage compounds by the formation of imine bonds opens the possibility to realize cages of different sizes, geometries, topologies, and functions. It is generally assumed that the imine bond is rather chemically labile allowing a self-correction mechanism until thermodynamic equilibrium is reached, which is o...
