2018
DOI: 10.1039/c8ob01158c
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A quantification scheme for non-covalent interactions in the enantio-controlling transition states in asymmetric catalysis

Abstract: The origin of enantioselectivity in asymmetric catalysis is attributed to the energy difference between lower and higher energy diastereomeric transition states, which are respectively responsible for the formation of major and minor enantiomers. Although the increase in the number of transition state models emphasizes the role of weak non-covalent interactions in asymmetric induction, the strength of such interactions is seldom quantified. Through this article, we propose a simple and effective method of quan… Show more

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Cited by 9 publications
(7 citation statements)
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“…Related to our approach, Sunoj and Toste counted the number and type of NCIs in the enantioselective Pd-phosphoric acid-catalyzed Heck–Matsuda arylation reaction . Sunoj has also used basis set superposition counterpoise calculations to estimate NCIs …”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…Related to our approach, Sunoj and Toste counted the number and type of NCIs in the enantioselective Pd-phosphoric acid-catalyzed Heck–Matsuda arylation reaction . Sunoj has also used basis set superposition counterpoise calculations to estimate NCIs …”
Section: Resultsmentioning
confidence: 99%
“…101 Sunoj has also used basis set superposition counterpoise calculations to estimate NCIs. 102 To confirm that our direct counting method provides an estimate of dispersion stabilization, for each new catalyst ethylene and 1-hexene migratory insertion transition state, the absolute difference in total dispersion energy was determined by energy evaluation with and without the D3(BJ) correction (|ΔDispE ‡ |)). We also counted the difference between the number of NCIs between the ethylene and 1-hexene transition states (ΔNCI).…”
Section: ■ Results and Discussionmentioning
confidence: 99%
“…To further distinguish the impact of NCIs involving the aromatic moiety of the alcohol, relative single point energies were calculated for TS2_HC structures, wherein the naphthyl moiety of 1 b was replaced by a hydrogen atom (see Figure 5). [32] While almost no energy difference is found for the H-capped structures TS2_HC (green bars in Figure 5), the NCI energy contribution (yellow bar in Figure 5) is very significant at À10.9 kJ mol À1 and thus the dominant component for the preference of the (R)-TS2_1. Similar trends were found for all of the other relevant conformers (see SI).…”
Section: Computational Studiesmentioning
confidence: 95%
“…Abbildung 5). [32] Während so gut wie kein Energieunterschied für die H-gedeckelten Strukturen TS2_HC (grüne Balken in Abbildung 5) gefunden wurde, unterscheiden sich die Energiebeiträge durch NKWs (gelbe Balken in Abbildung 5) erheblich um À10.9 kJ mol À1 und liefern somit den entscheidenden Beitrag zur Stabilität von (R)-TS2_1. Vergleichbare Tendenzen wurden für alle anderen relevanten Konformere gefunden (vgl.…”
Section: Methodsunclassified