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Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate
Author(s) -
Rotunno Giuseppe,
Petersen Dirk,
Amedjkouh Mohamed
Publication year - 2020
Publication title -
chemsystemschem
Language(s) - English
Resource type - Journals
ISSN - 2570-4206
DOI - 10.1002/syst.201900060
Subject(s) - autocatalysis , hemiacetal , hydride , chemistry , aldehyde , chirality (physics) , disproportionation , pyridine , derivative (finance) , alicyclic compound , photochemistry , stereochemistry , organic chemistry , catalysis , hydrogen , chiral symmetry , physics , nambu–jona lasinio model , quantum mechanics , financial economics , economics , quark
Abstract : In contrast to the homogenous phase, absolute asymmetric amplification of pyridine alkanol is observed under heterogenous conditions. The reaction of iPr 2 Zn vapor on a solid powder of pyridine carbaldehyde induced autocatalytic amplification of chirality providing the alkanol product with an enantiopurity up to 90 % ee. In this study, side products were identified and their formation is traced back to redox pathways involving hydride transfer, namely a chiral ester resulting most probably from a disproportionation of the starting aldehyde into a hemiacetal and subsequent hydride loss following a Claisen‐Tishchenko mechanism. These observations provide new perspectives in the elucidation of the mechanism of amplification of chirality in the Soai reaction.