Hydroxyoxiranone

An ab initio MO investigation of the structure and stability of a model for a possible α-lactone intermediate in hydrolysis of sialyl glycosides

Stuart Firth-Clark, Christopher F. Rodriquez, Ian H. Williams

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Abstract

The standard enthalpy of formation ΔH○f,298 for hydroxyoxiranone is estimated as -377 ± 10 kJ mol-1 by means of ab initio molecular orbital calculations at the QCISD(T)(full)/6-311G(2df,p)//MP2(full)/6-311G(d,p) level of theory, corresponding to a conventional ring strain energy of 104 kJ mol-1. The hydroxy substituent on Cα stabilizes the α-lactone by 65 kJ mol-1 with concomitant elongation of the bond from Cα to the endocyclic oxygen On. There is a much larger stabilization (205 kJ mol-1) by the hydroxy substituent upon the zwitterion obtained by heterolysis of the Cα-On bond, and upon the carbene obtained by decarboxylation of the zwitterion. The relative energies of the α-lactone, zwitterion and carbene have been determined by MP2(fc)/6-31+G(d) calculations in vacuo and with the IPCM method for aqueous solvation. Solvation by this continuum method preferentially stabilizes the zwitterion, although at the IPCM-MP2(fc)/6-31+G(d) level the a-lactone is still 21 kJ mol-1 lower in energy than the zwitterion.

Original languageEnglish
Pages (from-to)1943-1948
Number of pages6
JournalJournal of the Chemical Society. Perkin Transactions 2
Volume1997
Issue number10
DOIs
Publication statusPublished - 1 Jan 1997

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Hydroxyoxiranone: An ab initio MO investigation of the structure and stability of a model for a possible α-lactone intermediate in hydrolysis of sialyl glycosides",
abstract = "The standard enthalpy of formation ΔH○f,298 for hydroxyoxiranone is estimated as -377 ± 10 kJ mol-1 by means of ab initio molecular orbital calculations at the QCISD(T)(full)/6-311G(2df,p)//MP2(full)/6-311G(d,p) level of theory, corresponding to a conventional ring strain energy of 104 kJ mol-1. The hydroxy substituent on Cα stabilizes the α-lactone by 65 kJ mol-1 with concomitant elongation of the bond from Cα to the endocyclic oxygen On. There is a much larger stabilization (205 kJ mol-1) by the hydroxy substituent upon the zwitterion obtained by heterolysis of the Cα-On bond, and upon the carbene obtained by decarboxylation of the zwitterion. The relative energies of the α-lactone, zwitterion and carbene have been determined by MP2(fc)/6-31+G(d) calculations in vacuo and with the IPCM method for aqueous solvation. Solvation by this continuum method preferentially stabilizes the zwitterion, although at the IPCM-MP2(fc)/6-31+G(d) level the a-lactone is still 21 kJ mol-1 lower in energy than the zwitterion.",
author = "Stuart Firth-Clark and Rodriquez, {Christopher F.} and Williams, {Ian H.}",
year = "1997",
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journal = "Journal of the Chemical Society, Perkin Transactions 2",
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publisher = "Royal Society of Chemistry",
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T1 - Hydroxyoxiranone

T2 - An ab initio MO investigation of the structure and stability of a model for a possible α-lactone intermediate in hydrolysis of sialyl glycosides

AU - Firth-Clark, Stuart

AU - Rodriquez, Christopher F.

AU - Williams, Ian H.

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Y1 - 1997/1/1

N2 - The standard enthalpy of formation ΔH○f,298 for hydroxyoxiranone is estimated as -377 ± 10 kJ mol-1 by means of ab initio molecular orbital calculations at the QCISD(T)(full)/6-311G(2df,p)//MP2(full)/6-311G(d,p) level of theory, corresponding to a conventional ring strain energy of 104 kJ mol-1. The hydroxy substituent on Cα stabilizes the α-lactone by 65 kJ mol-1 with concomitant elongation of the bond from Cα to the endocyclic oxygen On. There is a much larger stabilization (205 kJ mol-1) by the hydroxy substituent upon the zwitterion obtained by heterolysis of the Cα-On bond, and upon the carbene obtained by decarboxylation of the zwitterion. The relative energies of the α-lactone, zwitterion and carbene have been determined by MP2(fc)/6-31+G(d) calculations in vacuo and with the IPCM method for aqueous solvation. Solvation by this continuum method preferentially stabilizes the zwitterion, although at the IPCM-MP2(fc)/6-31+G(d) level the a-lactone is still 21 kJ mol-1 lower in energy than the zwitterion.

AB - The standard enthalpy of formation ΔH○f,298 for hydroxyoxiranone is estimated as -377 ± 10 kJ mol-1 by means of ab initio molecular orbital calculations at the QCISD(T)(full)/6-311G(2df,p)//MP2(full)/6-311G(d,p) level of theory, corresponding to a conventional ring strain energy of 104 kJ mol-1. The hydroxy substituent on Cα stabilizes the α-lactone by 65 kJ mol-1 with concomitant elongation of the bond from Cα to the endocyclic oxygen On. There is a much larger stabilization (205 kJ mol-1) by the hydroxy substituent upon the zwitterion obtained by heterolysis of the Cα-On bond, and upon the carbene obtained by decarboxylation of the zwitterion. The relative energies of the α-lactone, zwitterion and carbene have been determined by MP2(fc)/6-31+G(d) calculations in vacuo and with the IPCM method for aqueous solvation. Solvation by this continuum method preferentially stabilizes the zwitterion, although at the IPCM-MP2(fc)/6-31+G(d) level the a-lactone is still 21 kJ mol-1 lower in energy than the zwitterion.

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