Journal article
Cyclic beta-hydroxy-alpha-nitrosulfone isomers readily interconvert via open-chain aldehyde forms
Organic & biomolecular chemistry, v 21(24), pp 5033-5039
21 Jun 2023
PMID: 37264923
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
Two structurally diverse cyclic beta-hydroxy-alpha-nitrosulfones have been prepared and their isomerisation reactions studied. These cyclic beta-hydroxy-alpha-nitrosulfones undergo isomer equilibration via open-chain aldehyde forms under a variety of mild conditions. Michael condensation of 1,1 '-[(1,3-dinitro-1,3-propanediyl)bis(sulfonyl)]bis(benzene) with propenal and subsequent cyclisation afforded 2,4-dinitro-2,4-bis(phenylsulfonyl)cyclohexanol in 98% yield as a mixture of four diastereomers. Sequential chromatography and recrystallization afford pure (1R,2R,4S)-rel-2,4-dinitro-2,4-bis(phenylsulfonyl)cyclohexanol based on spectroscopic and X-ray crystallographic data. This diastereomer equilibrates with the other three possible diastereomers under a variety of mild conditions: during silica gel chromatography, when dissolved in basic solution, and when dissolved in neutral polar solvents. Open-chain aldehyde forms are implicated as intermediates in isomer interconversion. Condensation of 1-methyl-4-[(nitromethyl)sulfonyl]benzene and pentanedial gives 2-(4-methylphenylsulfonyl)-2-nitrocyclohexane-1,3-diol as predominantly two diastereomers. Purification affords pure racemic diastereomer in 55% yield. This racemic diastereomer interconverts with several other isomers during silica gel chromatography. These isomers were identified as one, likely two, diastereomeric meso 2-(4-methylphenylsulfonyl)-2-nitrocyclohexane-1,3-diol isomers and four cyclic hemiacetal constitutional isomers. When dissolved in neutral polar solvents, the racemic diastereomer also interconverts with meso diastereomers and cyclic hemiacetals showing a marked solvent dependence. Reaction of the racemic diastereomer with triethylamine in dichloromethane results in isomerisation as well as substantial reversion to 1-methyl-4-[(nitromethyl)sulfonyl]benzene and pentanedial. Reaction with triethylamine in DMSO as well as simply warming in DMSO results in ring opening and concomitant dehydration to afford (E)-6-(4-methylphenylsulfonyl)-6-nitrohex-4-enal.
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Details
- Title
- Cyclic beta-hydroxy-alpha-nitrosulfone isomers readily interconvert via open-chain aldehyde forms
- Creators
- Peter A. Wade - Drexel UniversityRuchi Tandon - Drexel UniversityPatrick J. Carroll - University of Pennsylvania
- Publication Details
- Organic & biomolecular chemistry, v 21(24), pp 5033-5039
- Publisher
- Royal Soc Chemistry
- Number of pages
- 7
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- [Retired Faculty]; Chemistry
- Web of Science ID
- WOS:001009883200001
- Scopus ID
- 2-s2.0-85162250601
- Other Identifier
- 991021229986304721
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- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Organic