173068-91-2Relevant academic research and scientific papers
Structural contributions to autocatalysis and asymmetric amplification in the soai reaction
Athavale, Soumitra V.,Simon, Adam,Houk,Denmark, Scott E.
supporting information, p. 18387 - 18406 (2020/11/17)
Diisopropylzinc alkylation of pyrimidine aldehydes-the Soai reaction, with its astonishing attribute of amplifying asymmetric autocatalysis-occupies a unique position in organic chemistry and stands as an eminent challenge for mechanistic elucidation. A n
In Situ Mass Spectrometric and Kinetic Investigations of Soai's Asymmetric Autocatalysis
Lamour, Saskia,Maier, Frank,Siegle, Alexander F.,Straub, Bernd F.,Trapp, Oliver,Zawatzky, Kerstin
supporting information, (2020/10/19)
Chemical reactions that lead to a spontaneous symmetry breaking or amplification of the enantiomeric excess are of fundamental interest in explaining the formation of a homochiral world. An outstanding example is Soai's asymmetric autocatalysis, in which small enantiomeric excesses of the added product alcohol are amplified in the reaction of diisopropylzinc and pyrimidine-5-carbaldehydes. The exact mechanism is still in dispute due to complex reaction equilibria and elusive intermediates. In situ high-resolution mass spectrometric measurements, detailed kinetic analyses and doping with in situ reacting reaction mixtures show the transient formation of hemiacetal complexes, which can establish an autocatalytic cycle. We propose a mechanism that explains the autocatalytic amplification involving these hemiacetal complexes. Comprehensive kinetic experiments and modelling of the hemiacetal formation and the Soai reaction allow the precise prediction of the reaction progress, the enantiomeric excess as well as the enantiomeric excess dependent time shift in the induction period. Experimental structural data give insights into the privileged properties of the pyrimidyl units and the formation of diastereomeric structures leading to an efficient amplification of even minimal enantiomeric excesses, respectively.
Pyrimidine derivatives
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, (2008/06/13)
Pyrimidine derivatives useful as plant growth regulators and fungicides having the general formula (I): STR1 wherein Y is optionally substituted cyclopropyl or 1-methyl-cyclopropyl or is optionally halo-substituted isopropyl or t-butyl; R2 is a
Pyrimidine derivatives
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, (2008/06/13)
A pyrimidine derivative having the general formula (I): STR1 and stereoisomers thereof, wherein Y is optional substituted cyclopropyl or optionally substituted 1-methylcyclopropyl or is the group: STR2 wherein R1 is hydrogen or methyl; X is hydrogen or halogen; R2 is an optionally substituted alkyl, cycloalkyl, cycloalkylalkyl or alkylcycloalkyl group, each of said groups containing a total of from 4 to 8 carbon atoms; or is an optionally substituted alkenyl, cycloalkenyl, cycloalkenylalkyl, or alkylcycloalkenyl group, each of said groups containing a total of from 4 to 8 carbon atoms; or is an optionally substituted alkynyl group containing a total of from 4 to 8 carbon atoms; and R3 is hydrogen, an alkyl group containing from 1 to 4 carbon atoms, an alkenyl group containing from 3 to 4 carbon atoms or an alkynyl group containing from 3 to 4 carbon atoms; and agrochemically acceptable salts, esters and metal complexes of the compounds of formula (I) wherein R3 is hydrogen. These compounds are useful as plant growth regulating agents and fungicides.
Process for the preparation of 5-acylpyrimidines
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, (2008/06/13)
A process for the preparation of a 5-acylpyrimidine of the formula STR1 in which R is an organic radical comprising reacting a methyl ketone of the formula in a first stage with a formylating reagent in the presence of a base to form an enolketone of the
