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Synthesis 2022; 54(02): 355-368
DOI: 10.1055/a-1638-2478
DOI: 10.1055/a-1638-2478
feature
Kinetic Resolution by Lithiation: Highly Enantioselective Synthesis of Substituted Dihydrobenzoxazines and Tetrahydroquinoxalines
This work was supported by the Engineering and Physical Sciences Research Council (EPSRC, grant EP/R024294/1), the University of Sheffield, the Ministry of Higher Education and Scientific Research Libya, the Royal Society (Short Industry Fellowship SIF\R2\202031), and the Medical Research Council (MRC, grant MR/S009280/1).
Abstract
Kinetic resolution provided a highly enantioselective method to access a range of 3-aryl-3,4-dihydro-2H-1,4-benzoxazines using n-butyllithium and the chiral ligand sparteine. The enantioenrichment remained high on removing the tert-butoxycarbonyl (Boc) protecting group. The intermediate organolithium undergoes ring opening to an enamine. The kinetic resolution was extended to give enantiomerically enriched substituted 1,2,3,4-tetrahydroquinoxalines and was applied to the synthesis of an analogue of the antibiotic levofloxacin that was screened for its activity against the human pathogen Streptococcus pneumoniae.
Key words
ring opening - lithiation - kinetic resolution - heterocycles - enantioselectivity - elimination - antibioticsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1638-2478.
- Supporting Information
Publication History
Received: 20 August 2021
Accepted: 06 September 2021
Accepted Manuscript online:
06 September 2021
Article published online:
26 October 2021
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For spectroscopic data for compound 1a, see:
For related ring opening of lithiated intermediates, see:
Representative data for 3a–e: