Catalysis of α-Hydrogen Exchange. I. The Reaction of Isobutyraldehyde-2-d with Tertiary Amines and Oxygen Bases<sup>1a</sup>

Hine, Jack; Houston, James G.; Jensen, James H.; Mulders, Julien

doi:10.1021/ja00950a014

Cited by 31 publications

(14 citation statements)

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“…The high rate of the reaction catalysed by triose phosphate isomerase makes it a reasonable assumption that the substrates bind to the enzyme in the most favourable conformation for reaction. If this is the one in which the C-H bond being broken is perpendicular to the plane of the carbonyl group (Corey & Sneen, 1956;Hine, Houston, Jensen & Mulders, 1965) then the conformations leading to the ci8-enediol will be as shown [structures (I) and (II) in Fig. 3].…”

Section: Discussionmentioning

confidence: 99%

The active centre of rabbit muscle triose phosphate isomerase. The site that is labelled by glycidol phosphate

Miller

Waley

1971

Biochemical Journal

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1. Glycidol (2,3-epoxypropanol) phosphate is a specific irreversible inhibitor of rabbit muscle triose phosphate isomerase (EC 5.3.1.1); the site of attachment has now been studied. 2. The labelled enzyme was digested with pepsin and a modified peptide isolated. The sequence of the peptide is: Ala-Tyr-Glu-Pro-Val-Trp. 3. It is the glutamic acid residue in this peptide that is labelled: the peptide is thus a gamma-glutamyl ester derived from glycerol phosphoric acid. The same site is labelled by a mixture of glycidol and inorganic phosphate. 4. Kinetic and stereochemical features of these reactions are discussed.

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Section: Discussionmentioning

confidence: 99%

The active centre of rabbit muscle triose phosphate isomerase. The site that is labelled by glycidol phosphate

Miller

Waley

1971

Biochemical Journal

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“…Other geometrical parameters (ra values) are C-F = 1.329 (4) A, C-C = 1. 45 (2) A, S=C = 1.434 (14) A, S-F = 1.561 (3) A, FCF = 108.4 (5)°, and FSF = 93.2 (9)°. Ab initio calculations have been performed for HC==SF3, FC=SF3, CH3C=SF3, and CF3C=SF3.…”

Section: Cf3-c=sf3mentioning

confidence: 99%

Vinyl alcohol. Generation and decay kinetics in aqueous solution and determination of the tautomerization equilibrium constant and acid dissociation constants of the aldehyde and enol forms

Chiang¹,

Hojatti²,

Keeffe³

et al. 1987

J. Am. Chem. Soc.

134

105

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“…The interpretation, however, of some of these data in terms of the RSP has been questioned [15 J.A major criticism is that the presence of curvature depends strongly on the inclusion of points for the OH-/H20 or H 30+/H20 pairs into the correlation. In fact, enolization data have commonly been treated in this manner [18]. In fact, enolization data have commonly been treated in this manner [18].…”

Section: ] -Marcus [5] -Hammond [2a]--polanyi [6j-thornton [7j-lefflementioning

confidence: 99%

Ionization of Acetylacetone in Me₂SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Bernasconi

Bunnell

1985

Israel Journal of Chemistry

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Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me2SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me2SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pKa values measured in the respective solvents.) The intrinsic rate constant (k0) for proton transfer increases with the addition of Me2SO, and more so with the carboxylate buffers than with the amines. This increase in k0 is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).

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Catalysis of α-Hydrogen Exchange. I. The Reaction of Isobutyraldehyde-2-d with Tertiary Amines and Oxygen Bases^1a

Cited by 31 publications

References 0 publications

The active centre of rabbit muscle triose phosphate isomerase. The site that is labelled by glycidol phosphate

The active centre of rabbit muscle triose phosphate isomerase. The site that is labelled by glycidol phosphate

Vinyl alcohol. Generation and decay kinetics in aqueous solution and determination of the tautomerization equilibrium constant and acid dissociation constants of the aldehyde and enol forms

Ionization of Acetylacetone in Me₂SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

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Catalysis of α-Hydrogen Exchange. I. The Reaction of Isobutyraldehyde-2-d with Tertiary Amines and Oxygen Bases1a

Cited by 31 publications

References 0 publications

The active centre of rabbit muscle triose phosphate isomerase. The site that is labelled by glycidol phosphate

The active centre of rabbit muscle triose phosphate isomerase. The site that is labelled by glycidol phosphate

Vinyl alcohol. Generation and decay kinetics in aqueous solution and determination of the tautomerization equilibrium constant and acid dissociation constants of the aldehyde and enol forms

Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

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Catalysis of α-Hydrogen Exchange. I. The Reaction of Isobutyraldehyde-2-d with Tertiary Amines and Oxygen Bases^1a

Ionization of Acetylacetone in Me₂SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?