Models for two ketoreductases were created and used to predict the stereoselectivity of the enzymes. One was based on the crystal structure of Sporobolomyces salmonicolor. This model was used to predict the stereoselectivity for 46 ketone reductions using this enzyme; only 6 were incorrectly predicted. The stereochemistries of the products were compared to the experimental values found in the l...

In this study we have tested the ability of a standard DFT computational protocol to reproduce the experimentally obtained stereoselectivity of 26 different C2-symmetric zirconocene catalysts active in propylene polymerization. The catalysts were chosen for their relevance in metallocene catalyzed polymerization of propylene. To this end, primary insertion of both si- and re-propylene enantiofa...

Structure-guided design of substrate-binding pocket inversed the stereoselectivity of an NADH-dependent medium-chain alcohol dehydrogenase (MDR) from Prelog to anti-Prelog. The pocket-forming amino acids, especially the unconserved residues as hotspots, play critical roles in directing MDRs' stereoselectivity.

Addition of 5-substituted dithianyl anions to carbonyl compounds normally produces trans adducts. The presence of a nucleophilic hydroxymethyl group in position 5 dramatically decreases the trans stereoselectivity of the reaction in THF. The trans/cis ratio shows a bell curve dependence on HMPA, fitted to a quantitative model involving a series of equilibrated ion pairs, of which an intermediat...

Experiments on 3D-printed chiral active ellipsoids now uncover the dynamical analogs of stereoselectivity and self-recognition.

Nucleoside reverse transcriptase inhibitors (NRTIs) with L-stereochemistry have long been an effective treatment for viral infections because of the strong D-stereoselectivity exhibited by human DNA polymerases relative to viral reverse transcriptases. The D-stereoselectivity of DNA polymerases has only recently been explored structurally and all three DNA polymerases studied to date have demon...

DNA-templated synthesis is a surprisingly general strategy for controlling chemical reactivity that enables synthetic products to be manipulated in ways previously available only to biological macromolecules. The chiral nature of the DNA template raises the possibility that DNA-templated synthesis can proceed stereoselectively. Here, we show that DNA-templated substitution reactions can exhibit...

The catalytic asymmetric allylboration of cyclic imines with γ,γ-disubstituted allylboronic acids provides products with adjacent stereocenters in high yield and stereoselectivity. Various electrophiles, including 3,4-dihydroisoquinolines and indoles, were prenylated in a fully stereodivergent fashion by switching the E/Z geometry of the allylboronate and/or the enantiomer of the BINOL catalyst...

The asymmetric mixed carboligation of aldehydes with thiamine diphosphate (ThDP)-dependent enzymes is an excellent example where activity as well as changes in chemo- and stereoselectivity can be followed sensitively. To elucidate the influence of organic additives in enzymatic carboligation reactions of mixed 2-hydroxy ketones, we present a comparative study of six ThDP-dependent enzymes in 13...

Experimental data on the stereoselectivity of base-catalyzed 1,2-elimination reactions that produce conjugated carbonyl compounds are scarce in spite of the importance of these reactions in organic and biochemistry. As part of a comprehensive study in this area, we have synthesized stereospecifically-deuterated beta-tosyloxybutanoate esters and thioesters and studied the stereoselectivity of th...