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High‐Pressure‐Mediated Thiourea‐Organocatalyzed Asymmetric Michael Addition to (Hetero)aromatic Nitroolefins: Prediction of Reaction Parameters by PCP‐SAFT Modelling
Author(s) -
Weinbender Thomas,
Knierbein Michael,
Bittorf Lukas,
Held Christoph,
Siewert Riko,
Verevkin Sergey P.,
Sadowski Gabriele,
Reiser Oliver
Publication year - 2020
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.202000364
Subject(s) - diethyl malonate , michael reaction , chemistry , thiourea , high pressure , hydrostatic pressure , organic chemistry , thermodynamics , computational chemistry , catalysis , physics
Thiourea‐organocatalyzed Michael additions of diethyl malonate to various heteroaromatic nitroolefins (13 examples) have been studied under high‐pressure (up to 800 MPa) and ambient pressure conditions. High pressure was conducive to enhanced product yields by a factor of 2–12 at a given reaction time, high reaction rates (reaction times were decreased from 72–24 h down to 4–24 h) and high enantioselectivity. Elucidating the effects of solvents for maximizing reaction rates and yields has been carried out using the Perturbed‐Chain Polar Statistical Associating Fluid Theory (PCP‐SAFT), allowing for the first time a prediction of the kinetic profiles under high‐hydrostatic‐pressure conditions.