reaction of dialkyl acetylenedicarboxylates 1a-c andpyrrole derivatives 2a-e in the presence of triphenylphosphite (tpp) was investigated and the effect of the pyrrole substitution was established. diastereoselectivity is observed with pyrroles, 2a,b, yieldingphosphonate ester derivatives 3a-f and 4,and their relative configuration is determined by 1h/13c and 31p nmr and confirmed by single x-r...

The [2 + 2] cycloadditions of thioketenes and imines are named as thio-Staudinger cycloadditions. The diastereoselectivity in thio-Staudinger cycloaddtions of alkyl/alkenyl/aryl-substituted thioketenes is rationalized. The steric effects of the thioketenes play an extremely important role in deciding the diastereoselectivity (cis/trans selectivity) through controlling exo- and endo-attack and s...

This study was aimed at determining the effect, if any, that steric factors may have on the diastereoselectivity in the spiroannulation of simple phenols. A series of phenols bearing different size substituents ortho to the phenolic hydroxyl were synthesized and spiroannulated to the corresponding spiroethers in good to excellent yields (76-94%). However, the diastereoselectivity of the reactio...

Reaction of dialkyl acetylenedicarboxylates 1a-c andpyrrole derivatives 2a-e in the presence of triphenylphosphite (TPP) was investigated and the effect of the pyrrole substitution was established. Diastereoselectivity is observed with pyrroles, 2a,b, yieldingphosphonate ester derivatives 3a-f and 4,and their relative configuration is determined by 1H/13C and 31</...

Diastereoselective Ugi reactions of DMAP-based aldehydes with α-amino acids and tert-butyl isocyanide were examined. The reactions of 4-(dimethylamino)-2-pyridinecarboxaldehyde with various α-amino acids afforded 2-substituted DMAP derivatives with low diastereoselectivity. On the contrary, reactions with 4-(dimethylamino)-3-pyridinecarboxaldehyde delivered 3-substituted DMAP derivatives with m...

High diastereoselectivity is observed in the preparation of configurationally stable allocolchicinoids 5 from Fischer carbene complexes 4 and 1-pentyne. The analogous reaction of complexes 8 gives 9 with moderate diastereoselectivity for the opposite atropisomer and this selectivity can be taken to high levels under thermodynamic conditions.

During the synthesis of the new antimalarial drug candidate NITD609, a high degree of diastereoselectivity was observed in the Pictet-Spengler reaction. By isolating both the 4E and 4Z imine intermediates, a systematic mechanistic study of the reaction under both kinetic and thermodynamic conditions was conducted. This study provides insight into the source of the diastereoselectivity for this ...

Palladium-catalyzed oxidative cyclization of alkenols provides a convenient entry into cyclic ethers but typically proceeds with little or no diastereoselectivity for cyclization of trisubstituted olefins to form tetrahydrofurans due to the similar energies of competing 5-membered transition-state conformations. Herein, a new variant of this reaction has been developed in which a PdCl2/1,4-benz...

The purpose of this study was to explore a series of Passerini reactions on a biocatalytically derived enantiopure azetidine-2-carboxyaldehyde in order to obtain, in a diastereoselective manner, polyfunctionalised derivatives having the potential to be cyclized to chiral bridged bicyclic nitrogen heterocycles. While diastereoselectivity was poor under classical Passerini conditions, a significa...

As the first step to understand the reaction mechanism and diastereoselectivity of sodium borohydride reduction of ketones, ab initio Car-Parrinello molecular dynamics simulation has been performed on a solution of NaBH4 in liquid methanol. According to pointwise thermodynamic integration involving constrained molecular dynamics simulations, it was strongly suggested that Na+ and BH4(-) are ass...