Mechanism of the asymmetric autocatalytic Soai reaction studied by density functional theory

Chemistry : a European Journal
Luca Schiaffino, Gianfranco Ercolani

Abstract

The mechanism of the Soai reaction has been thoroughly investigated at the M05-2X/6-31G(d) level of theory, by considering ten energetically distinct paths. The study indicates the fully enantioselective catalytic cycle of the homochiral dimers to be the dominant mechanism. Two other catalytic cycles are shown to both be important for correct understanding of the Soai reaction. These are the catalytic cycle of the heterochiral dimer and the non-enantioselective catalytic cycle of the homochiral dimers. The former has been proved to be not really competitive with the principal cycle, as required for the Soai reaction to manifest chiral amplification, whereas the latter, which is only slightly competitive with the principal one, nicely explains the experimental enantioselectivity observed in the reaction of 2-methylpyrimidine-5-carbaldehyde. The study has also evidenced the inadequacy of the B3LYP functional for mechanistic investigations of the Soai reaction.

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Citations

Feb 11, 2015·Chemical Communications : Chem Comm·Masanori ShigenoMasahiko Yamaguchi
Oct 28, 2014·Chemistry : a European Journal·Guillem ValeroAlbert Moyano
Jun 23, 2018·Chemistry : a European Journal·Aleksandra A AgeevaTatyana V Leshina
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Oct 15, 2010·Journal of the American Chemical Society·Michela QuarantaDonna G Blackmond
Mar 16, 2011·The Journal of Organic Chemistry·Gianfranco Ercolani, Luca Schiaffino
Oct 9, 2021·Chemical Communications : Chem Comm·Arimasa MatsumotoKenso Soai

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