Synthesis
DOI: 10.1055/a-1683-0484
paper

The Application of 1,2-Oxazinanes as Chiral Cyclic Weinreb Amide-Type Auxiliaries Leading to a Three-Component, One-Pot Reaction

Jan Fährmann
,
Ludmila Hermann
,


Abstract

1,2-Oxazines were synthesised via a copper-catalysed aerobic acyl nitroso Diels–Alder reaction from 1,4-disubstituted 1,3-dienes and N-Boc-hydroxylamine. From this, 1,2-oxazinanes were obtained in a novel follow-up reaction path. The stability of several 1,2-oxazines and 1,2-oxazinanes towards organometallic compounds was tested to rate their operability as cyclic chiral Weinreb amide auxiliaries. 3,6-Di-tert-butyl-1,2-oxazinane gave the best results and was introduced as a chiral Weinreb amide-type auxiliary to yield chiral α-substituted ketones in a diastereomeric ratio of up to 98:2. The removal of the auxiliary can be performed with BuLi to form unsymmetrical α-chiral ketones. Thereafter, the chiral auxiliary can be re-isolated and purified by sublimation under vacuum.

Supporting Information



Publication History

Received: 23 August 2021

Accepted after revision: 29 October 2021

Publication Date:
29 October 2021 (online)

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
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