Highly effective and recyclable chiral auxiliaries: a study of the synthesis and use of three 4-isopropyl-5,5- diaryloxazolidin-2-ones

Karen Alexander, Stuart Cook, Colin L. Gibson, Alan R. Kennedy

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

A series of three 5,5-diaryl substituted oxazolidin-2-ones (diphenyl, dinaphthyl and ditolyl) have been synthesised. Studies on the benzylation of the lithium enolates of N-acyl derivatives reveal that the yields obtained were sensitive to the method of quenching the reaction. This was particularly acute for the 5,5-diphenyl system where effective yields (69%) and high diastereoselectivities (dr 98 2) are only observed when the reactions were quenched into aqueous buffer. Methylation studies on the N-acyl derivatives showed that the most advantageous results (58-69%, dr 91 9) were only observed using the sodium enolates. The 5,5-ditolyl-4-isopropyloxazolidin-2-one proved to be more efficacious in terms of efficiency and diastereoselectivity (dr 97 3). Subsequent, simple alkaline hydrolyses of the alkylation products allowed for the high recovery and recyclability of the 5,5-diaryl substituted oxazolidin-2-ones without any deleterious endocyclic cleavage. In addition, the acyl portions were recovered in high yield from the alkaline hydrolyses without any evidence of racemisation.
LanguageEnglish
Pages1538-1549
Number of pages11
JournalJournal of the Chemical Society, Perkin Transactions 1
Volume2001
Issue number13
DOIs
Publication statusPublished - 8 Jun 2001

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Oxazolidinones
Hydrolysis
Derivatives
Methylation
Alkylation
Lithium
Quenching
Buffers
Sodium
Recovery
diphenyl

Keywords

  • benzylation
  • lithium enolates
  • diastereoselectivities
  • aqueous buffer
  • recyclability

Cite this

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title = "Highly effective and recyclable chiral auxiliaries: a study of the synthesis and use of three 4-isopropyl-5,5- diaryloxazolidin-2-ones",
abstract = "A series of three 5,5-diaryl substituted oxazolidin-2-ones (diphenyl, dinaphthyl and ditolyl) have been synthesised. Studies on the benzylation of the lithium enolates of N-acyl derivatives reveal that the yields obtained were sensitive to the method of quenching the reaction. This was particularly acute for the 5,5-diphenyl system where effective yields (69{\%}) and high diastereoselectivities (dr 98 2) are only observed when the reactions were quenched into aqueous buffer. Methylation studies on the N-acyl derivatives showed that the most advantageous results (58-69{\%}, dr 91 9) were only observed using the sodium enolates. The 5,5-ditolyl-4-isopropyloxazolidin-2-one proved to be more efficacious in terms of efficiency and diastereoselectivity (dr 97 3). Subsequent, simple alkaline hydrolyses of the alkylation products allowed for the high recovery and recyclability of the 5,5-diaryl substituted oxazolidin-2-ones without any deleterious endocyclic cleavage. In addition, the acyl portions were recovered in high yield from the alkaline hydrolyses without any evidence of racemisation.",
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Highly effective and recyclable chiral auxiliaries: a study of the synthesis and use of three 4-isopropyl-5,5- diaryloxazolidin-2-ones. / Alexander, Karen; Cook, Stuart; Gibson, Colin L.; Kennedy, Alan R.

In: Journal of the Chemical Society, Perkin Transactions 1, Vol. 2001, No. 13, 08.06.2001, p. 1538-1549.

Research output: Contribution to journalArticle

TY - JOUR

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AB - A series of three 5,5-diaryl substituted oxazolidin-2-ones (diphenyl, dinaphthyl and ditolyl) have been synthesised. Studies on the benzylation of the lithium enolates of N-acyl derivatives reveal that the yields obtained were sensitive to the method of quenching the reaction. This was particularly acute for the 5,5-diphenyl system where effective yields (69%) and high diastereoselectivities (dr 98 2) are only observed when the reactions were quenched into aqueous buffer. Methylation studies on the N-acyl derivatives showed that the most advantageous results (58-69%, dr 91 9) were only observed using the sodium enolates. The 5,5-ditolyl-4-isopropyloxazolidin-2-one proved to be more efficacious in terms of efficiency and diastereoselectivity (dr 97 3). Subsequent, simple alkaline hydrolyses of the alkylation products allowed for the high recovery and recyclability of the 5,5-diaryl substituted oxazolidin-2-ones without any deleterious endocyclic cleavage. In addition, the acyl portions were recovered in high yield from the alkaline hydrolyses without any evidence of racemisation.

KW - benzylation

KW - lithium enolates

KW - diastereoselectivities

KW - aqueous buffer

KW - recyclability

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