Journal article

Structure-reactivity correlations of the abnormal Beckmann reaction of dihydrolevoglucosenone oxime

Amani Alhifthi, Benjamin L Harris, Lars Goerigk, Jonathan M White, Spencer J Williams

ORGANIC & BIOMOLECULAR CHEMISTRY | ROYAL SOC CHEMISTRY | Published : 2017

Abstract

A structural, spectroscopic and computational study of a series of oximes was undertaken to investigate how geometric and structural changes relevant to the reaction coordinate for the Beckmann reaction (normal Beckmann) and Beckmann fragmentation (abnormal Beckmann) manifest in the ground state. X-ray structures of a range of oximes derived from dihydrolevoglucosan (Cyrene™; which undergoes the abnormal Beckmann reaction), in which the oxygen substituent was systematically varied were determined. As the electron demand of the OR group increased, the major structural changes included lengthening of the N-OR bond distance, and a decrease in the magnitude of the C2[double bond, length as m-das..

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Grants

Awarded by ARC


Awarded by ARC DECRA Fellow


Awarded by University of Melbourne, Melbourne Bioinformatics


Awarded by National Computational Infrastructure Facility in Canberra through the National Computational Merit Allocation Scheme


Funding Acknowledgements

We thank the Australian Research Council (ARC) for financial support. SJW is an ARC-funded Future Fellow (FT130100103), and LG received support as an ARC DECRA Fellow (DE140100550). AA is grateful to Jazan University for financial support and thanks the Saudi Arabian Cultural Mission (SACM). LG is also grateful for generous allocation of computer time and technical support by The University of Melbourne, Melbourne Bioinformatics (project RA0005), and the National Computational Infrastructure Facility in Canberra through the National Computational Merit Allocation Scheme (project fk5). We thank Circa Group for a generous gift of Cyrene.