Rate enhancement of nucleophilic substitution reactions in phosphate esters. Influence of conformational transmission on the rate of solvolysis in alkyl diphenylphosphinates

Keijzer, de Aeh; Koole, Leo Lh; Hofstad, van der Wjm; Buck, HM Henk

doi:10.1021/jo00267a044

Cited by 16 publications

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“…Recently, de Keijzer et al [39,40] found that the solvolysis of phosphates is accelerated in systems where conformational transmission is possible. They showed that this is due to a stabilization of the transient trigonal bipyramid that allows conformational changes in the leaving group located in the axis of the trigonal bipyramid.…”

Section: Discussionmentioning

confidence: 99%

Conformational transmission in condensed lipid model compounds

Meulendijks

Haan

Genderen

et al. 1989

European Journal of Biochemistry

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On changing the phosphorus coordination from four to five via a trigonal bipyramidal geometry in phospholipid model systems, a conformational change is initiated around the C2-C3 linkage caused by enhanced electrostatic repulsion between the atoms 0 3 and 0 2 , situated in the axis of the trigonal bipyramid. This is supported by the absence ofconformational change upon substitution of 0 2 by methylene. With solid-state cross-polarization and magic-angle spinning 13C-NMR it is shown that such a conformational transmission leads to an increased packing density of the lipid chains. It seems to us that changes in lipid packing caused by conformational transmission may also occur when pentacoordination is present transiently, as under biological conditions, thereby inducing an activation of the transport proteins that are embedded in the membrane.

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Section: Discussionmentioning

confidence: 99%

Conformational transmission in condensed lipid model compounds

Meulendijks

Haan

Genderen

et al. 1989

European Journal of Biochemistry

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Solvent effects on reactions of hydroxide ion with phosphorus(V) esters. A quantitative treatment

Bunton

Gillitt

Kumar

1996

J. Phys. Org. Chem.

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Second‐order rate constants of reactions of HO− with phosphate, phosphinate and thiophosphinate esters, (PhO)2PO.OC6H4NO2‐p, Ph2PO.OC6H4NO2‐p, Ph2PO.SPh, Ph2PO.SC6H4NO2‐p and Ph2PO.SEt, go through minima with decreasing water content of H2O‐MeCN or H2O‐t‐BuOH. The rate decrease is due to stabilization of the non‐ionic ester on addition of organic solvent to H2O. This inhibition is partially offset by stabilization of the anionic transition states and in the drier solvents partial desolvation of HO− increases rates.

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Solvent Effects on Reactions of Hydroxide and Oximate Ions With Phosphorus(v) Esters

Burton

Gillitt

Kumar

1997

J. Phys. Org. Chem.

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Second-order rate constants of reactions of OHϪ , 2,3-butanedionemonooximate and 2-hydroxybenzaldoximate ions with aryl phosphate, phosphinate and thioarylphosphinate esters go through minima with decreasing water content of aqueous acetonitrile, tert-butyl alcohol and N-methyl-2-pyrrolidone. For reactions in H 2 O-MeCN the solvent effects are analyzed in terms of activity coefficients of the anionic nucleophiles and transition states. In the drier solvents partial desolvation of the nucleophiles increases rates. Nucleophilicities of several oximates and inorganic anions are compared in water.

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Rate enhancement of nucleophilic substitution reactions in phosphate esters. Influence of conformational transmission on the rate of solvolysis in alkyl diphenylphosphinates

Cited by 16 publications

References 0 publications

Conformational transmission in condensed lipid model compounds

Conformational transmission in condensed lipid model compounds

Solvent effects on reactions of hydroxide ion with phosphorus(V) esters. A quantitative treatment

Solvent Effects on Reactions of Hydroxide and Oximate Ions With Phosphorus(v) Esters

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