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

15 February 2018, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

Asymmetric Catalysis
Azetidine
Copper
Ligand
XRD
Computational
Henry Reaction
Platinum complex
Copper-catalysed

Supplementary materials

Title
Description
Actions
Title
Compound 1d AY3-350
Description
Actions
Title
Compound 11 ANTb121
Description
Actions

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