Stereoelectronic Control in Carbon-Oxygen and Phosphorus-Oxygen Bond Breaking Processes. Ab Initio Calculations and Speculations on the Mechanism of Action of Ribonuclease A, Staphylococcal Nuclease, and Lysozyme

David G. Gorenstein; John B. Findlay; Bruce A. Luxon; Debojyoti Kar

doi:10.1021/ja00452a047

Stereoelectronic Control in Carbon-Oxygen and Phosphorus-Oxygen Bond Breaking Processes. Ab Initio Calculations and Speculations on the Mechanism of Action of Ribonuclease A, Staphylococcal Nuclease, and Lysozyme

David G. Gorenstein
, John B. Findlay
, Bruce A. Luxon
, Debojyoti Kar

Research output: Contribution to journal › Article › peer-review

96 Scopus citations

Abstract

Ab initio molecular orbital calculations on dimethyl phosphate monoanion and dimethoxymethane demonstrate that antiperiplanar ester oxygen lone pairs significantly perturb the X-O (X = P or C) bond overlap populations. Specifically molecules in a gauche, trans conformation are “activated” for cleavage of the trans X-O bond. Other consequences of this torsional activation are discussed and presented in the context of a mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme.

Original language	English (US)
Pages (from-to)	3473-3479
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	99
Issue number	10
DOIs	https://doi.org/10.1021/ja00452a047
State	Published - 1977
Externally published	Yes

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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Gorenstein, D. G., Findlay, J. B., Luxon, B. A., & Kar, D. (1977). Stereoelectronic Control in Carbon-Oxygen and Phosphorus-Oxygen Bond Breaking Processes. Ab Initio Calculations and Speculations on the Mechanism of Action of Ribonuclease A, Staphylococcal Nuclease, and Lysozyme. Journal of the American Chemical Society, 99(10), 3473-3479. https://doi.org/10.1021/ja00452a047

Stereoelectronic Control in Carbon-Oxygen and Phosphorus-Oxygen Bond Breaking Processes. Ab Initio Calculations and Speculations on the Mechanism of Action of Ribonuclease A, Staphylococcal Nuclease, and Lysozyme. / Gorenstein, David G.; Findlay, John B.; Luxon, Bruce A. et al.
In: Journal of the American Chemical Society, Vol. 99, No. 10, 1977, p. 3473-3479.

Research output: Contribution to journal › Article › peer-review

Gorenstein, DG, Findlay, JB, Luxon, BA & Kar, D 1977, 'Stereoelectronic Control in Carbon-Oxygen and Phosphorus-Oxygen Bond Breaking Processes. Ab Initio Calculations and Speculations on the Mechanism of Action of Ribonuclease A, Staphylococcal Nuclease, and Lysozyme', Journal of the American Chemical Society, vol. 99, no. 10, pp. 3473-3479. https://doi.org/10.1021/ja00452a047

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abstract = "Ab initio molecular orbital calculations on dimethyl phosphate monoanion and dimethoxymethane demonstrate that antiperiplanar ester oxygen lone pairs significantly perturb the X-O (X = P or C) bond overlap populations. Specifically molecules in a gauche, trans conformation are “activated” for cleavage of the trans X-O bond. Other consequences of this torsional activation are discussed and presented in the context of a mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme.",

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AU - Findlay, John B.

AU - Luxon, Bruce A.

AU - Kar, Debojyoti

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AB - Ab initio molecular orbital calculations on dimethyl phosphate monoanion and dimethoxymethane demonstrate that antiperiplanar ester oxygen lone pairs significantly perturb the X-O (X = P or C) bond overlap populations. Specifically molecules in a gauche, trans conformation are “activated” for cleavage of the trans X-O bond. Other consequences of this torsional activation are discussed and presented in the context of a mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme.

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Stereoelectronic Control in Carbon-Oxygen and Phosphorus-Oxygen Bond Breaking Processes. Ab Initio Calculations and Speculations on the Mechanism of Action of Ribonuclease A, Staphylococcal Nuclease, and Lysozyme

Abstract

ASJC Scopus subject areas

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