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Rigid and concave, 2,4-cis-substituted azetidine derivatives: A platform for asymmetric catalysis

preprint
submitted on 14.02.2018 and posted on 15.02.2018 by Akina Yoshizawa, Antonio Feula, Louise Male, Andrew G. Leach, John Fossey
A series of single enantiomer, 2,4-cis-disubstituted amino azetidines were synthesised and used as ligands for copper-catalysed Henry reactions of aldehydes with nitromethane. Optimisation of ligand substituents and the reaction conditions was conducted. The enantiomeric excess of the formed products was highest when alkyl aldehydes were employed in the reaction (>99% e.e.). The absolute stereochemistry of one representative azetidine derivative salt was determined by analysis of the Flack parameter of an XRD single crystal structure. The origin of selectivity in catalysis was investigated computationally, revealing the importance of the amino-substituent in determining the stereochemical outcome. A racemic platinum complex of a cis-disubstituted azetidine is examined by XRD single crystal structure analysis with reference to its steric parameters, and analogies to the computationally determined copper complex catalyst are drawn.

Funding

EPSRC EP/J003220/1, Royal Society

History

Email Address of Submitting Author

j.s.fossey@bham.ac.uk

Email Address(es) for Other Author(s)

AXY212@bham.ac.uk, feula.antonio@gmail.com, L.Male@bham.ac.uk, a.g.leach@ljmu.ac.uk

Institution

University of Birmingham

Country

United Kingdom

ORCID For Submitting Author

0000-0002-2626-5117

Declaration of Conflict of Interest

None

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