scholarly journals Structural Contributions to Autocatalysis and Asymmetric Amplification in the Soai Reaction

2020 ◽  
Vol 142 (43) ◽  
pp. 18387-18406
Author(s):  
Soumitra V. Athavale ◽  
Adam Simon ◽  
K. N. Houk ◽  
Scott E. Denmark
Keyword(s):  
Soai Reaction

Prediction of Soai Reaction Enantioselectivity Induced by Crystals of N-(2-Thienylcarbonyl)glycine

2012 ◽  
Vol 12 (4) ◽  
pp. 2138-2145 ◽  
Author(s):  
Damien J. Carter ◽  
Andrew L. Rohl ◽  
Alexander Shtukenberg ◽  
Shudan Bian ◽  
Chunhua Hu ◽  
...  
Keyword(s):  
Soai Reaction

On the Origin and Structure of the Recently Observed Acetal in the Soai Reaction

2015 ◽  
Vol 88 (2) ◽  
pp. 333-340 ◽  
Author(s):  
Ilya D. Gridnev ◽  
Andrey Kh. Vorobiev
Keyword(s):  
Soai Reaction

scholarly journals Demystifying the Soai Reaction

2019 ◽  
Author(s):  
Soumitra Athavale ◽  
Adam Simon ◽  
Kendall N. Houk ◽  
Scott Denmark
Keyword(s):  
Density Functional ◽  
Spectroscopic Analysis ◽  
Chiral Symmetry Breaking ◽  
Kinetic Studies ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Group Transfer ◽  
Linear Behavior ◽  
Structural Mutations ◽  
Soai Reaction

The extraordinary Soai reaction has profoundly impacted chemists’ perspective of chiral symmetry breaking, absolute asymmetric synthesis and its role in the origin of biological homochirality. Herein, we describe the unprecedented observation of asymmetry amplifying autocatalysis in the alkylation of 5-(trimethylsilylethynyl)pyridine-3-carbaldehyde using diisopropylzinc. Kinetic studies with a “Trojan-horse” substrate and spectroscopic analysis of a series of zinc-alkoxides that incorporate specific structural mutations reveal a ‘pyridine-assisted cube escape’. The new cluster functions as a catalyst that activates the ‘floor-to-floor’ bound aldehyde and poises a coordinated diisopropylzinc moiety for alkyl group transfer. Transitionstate models leading to both the homochiral and heterochiral products were validated by density functional theory calculations. Moreover, experimental and computational analysis of the heterochiral complex provides a definitive explanation for the non-linear behavior of this system. Our deconstruction of the Soai system contributes substantially to understanding the mechanism of this transformation that has stood as a longstanding challenge in chemistry.<br>

scholarly journals Structural Contributions to Autocatalysis and Asymmetric Amplification in the Soai Reaction

2020 ◽  
Author(s):  
Soumitra Athavale ◽  
Adam Simon ◽  
Kendall N Houk ◽  
Scott Denmark
Keyword(s):  
Organic Chemistry ◽  
Substrate Binding ◽  
New Paradigm ◽  
Unique Position ◽  
Structure Activity ◽  
Alkyl Groups ◽  
Mixed Catalyst ◽  
Substrate Reactivity ◽  
Asymmetric Autocatalysis ◽  
Soai Reaction

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 new paradigm of ‘mixed catalyst substrate’ experiments with pyrimidine and pyridine systems allows a disconnection of catalysis from autocatalysis, providing insights into the role played by reactant and alkoxide structure. The alkynyl substituent favorably tunes catalyst solubility, aggregation and conformation while modulating substrate reactivity and selectivity. The alkyl groups and the heteroaromatic core play further complementary roles in catalyst aggregation and substrate binding. In the study of these structure activity relationships, novel pyridine substrates demonstrating amplifying autocatalysis were identified. Comparison of three autocatalytic systems representing a continuum of nitrogen Lewis basicity strength suggests how the strength of N-Zn binding events is a predominant contributor towards the rate of autocatalytic progression.<br><div> </div>

scholarly journals Mirror-symmetry breaking in the Soai reaction: A kinetic understanding

2005 ◽  
Vol 102 (39) ◽  
pp. 13743-13748 ◽  
Author(s):  
J. R. Islas ◽  
D. Lavabre ◽  
J.-M. Grevy ◽  
R. H. Lamoneda ◽  
H. R. Cabrera ◽  
...  
Keyword(s):  
Symmetry Breaking ◽  
Mirror Symmetry ◽  
Soai Reaction
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