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Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses

Ballard, Andrew ; Ahmad, Hiwa O. ; Narduolo, Stefania ; Rosa, Lucy ; Chand, Nikki ; Cosgrove, David A. ; Varkonyi, Peter ; Asaad, Nabil ; Tomasi, Simone ; Buurma, Niklaas J. ; Leach, Andrew G.

Angewandte Chemie, 2018-01, Vol.130 (4), p.994-997 [Periódico revisado por pares]

Weinheim: Wiley Subscription Services, Inc

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Título:
Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses
Autor: Ballard, Andrew ; Ahmad, Hiwa O. ; Narduolo, Stefania ; Rosa, Lucy ; Chand, Nikki ; Cosgrove, David A. ; Varkonyi, Peter ; Asaad, Nabil ; Tomasi, Simone ; Buurma, Niklaas J. ; Leach, Andrew G.
Assuntos: Biological properties ; Chemical compounds ; Circular dichroism ; Computerchemie ; Correlation analysis ; Dichroism ; Kinetics ; Mathematical analysis ; Quantum mechanics ; Racemisierung ; Racemization ; Rate constants ; Reaction kinetics ; Reaktionskinetik ; Spectroscopy ; Stereoselektive Synthese ; Wirkstoffentwicklung
É parte de: Angewandte Chemie, 2018-01, Vol.130 (4), p.994-997
Descrição: Racemization has a large impact upon the biological properties of molecules but the chemical scope of compounds with known rate constants for racemization in aqueous conditions was hitherto limited. To address this remarkable blind spot, we have measured the kinetics for racemization of 28 compounds using circular dichroism and 1H NMR spectroscopy. We show that rate constants for racemization (measured by ourselves and others) correlate well with deprotonation energies from quantum mechanical (QM) and group contribution calculations. Such calculations thus provide predictions of the second‐order rate constants for general‐base‐catalyzed racemization that are usefully accurate. When applied to recent publications describing the stereoselective synthesis of compounds of purported biological value, the calculations reveal that racemization would be sufficiently fast to render these expensive syntheses pointless. Das Racemisierungspotential komplexer organischer Moleküle wurde mithilfe einfacher quantenmechanischer Rechnungen und einem Gruppenadditivitätsschema vorhergesagt. Organochemiker können damit erst überprüfen, ob vorgegebene Syntheseziele strukturell stabil sind, bevor sie eine potentiell langwierige und kostenintensive chirale Synthese beginnen.
Editor: Weinheim: Wiley Subscription Services, Inc
Idioma: Inglês;Alemão

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Quantitative Prediction of Rate Constants for Aqueous Racemization To Avoid Pointless Stereoselective Syntheses

Ballard, Andrew ; Ahmad, Hiwa O. ; Narduolo, Stefania ; Rosa, Lucy ; Chand, Nikki ; Cosgrove, David A. ; Varkonyi, Peter ; Asaad, Nabil ; Tomasi, Simone ; Buurma, Niklaas J. ; Leach, Andrew G.

Weinheim: Wiley Subscription Services, Inc

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