Stereochemistry of piperazine-2,5-dione formation by self-condensation of DL-amino acid esters

Hiroshi Naraoka, Kaoru Harada

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5 Citations (Scopus)

Abstract

'Racemic' piperazine-2,5-diones (diketopiperazines, dkps) have been synthesized by the self-condensation of DL-amino acid esters without solvent. It was found that 'racemic' dkps consisted of cis-and trans-isomers, and that cis-dkp was preferentially formed in the early stage of the self-condensation, the cis:trans ratios gradually decreasing with increasing reaction time. These results may be attributed to the difference in the rates of cyclization of two kinds of diastereoisomeric dipeptide esters, intermediates in the formation of dkps from DL-amino acid esters. It was further confirmed that the pre-cis-dipeptide ester, which formed cis-dkp, cyclized faster than the pre-trans-dipeptide ester in methanol. Differences in steric hindrance in the cyclization reaction of pre-cis- and pre-trans-isomers may be an important factor in the stereochemistry of self-condensation.

Original languageEnglish
Pages (from-to)1557-1560
Number of pages4
JournalJournal of the Chemical Society, Perkin Transactions 1
Publication statusPublished - Dec 1 1986

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Stereochemistry
Diketopiperazines
Condensation
Esters
Dipeptides
Amino Acids
Cyclization
Isomers
Methanol
piperazine

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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T1 - Stereochemistry of piperazine-2,5-dione formation by self-condensation of DL-amino acid esters

AU - Naraoka, Hiroshi

AU - Harada, Kaoru

PY - 1986/12/1

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N2 - 'Racemic' piperazine-2,5-diones (diketopiperazines, dkps) have been synthesized by the self-condensation of DL-amino acid esters without solvent. It was found that 'racemic' dkps consisted of cis-and trans-isomers, and that cis-dkp was preferentially formed in the early stage of the self-condensation, the cis:trans ratios gradually decreasing with increasing reaction time. These results may be attributed to the difference in the rates of cyclization of two kinds of diastereoisomeric dipeptide esters, intermediates in the formation of dkps from DL-amino acid esters. It was further confirmed that the pre-cis-dipeptide ester, which formed cis-dkp, cyclized faster than the pre-trans-dipeptide ester in methanol. Differences in steric hindrance in the cyclization reaction of pre-cis- and pre-trans-isomers may be an important factor in the stereochemistry of self-condensation.

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