论文信息 - Stereoelectronic control of the tertiary ketol rearrangement: implications for the mechanism of the reaction catalysed by the enzymes of branched-chain amino acid metabolism, reductoisomerase and acetolactate decarboxylase

Stereoelectronic control of the tertiary ketol rearrangement: implications for the mechanism of the reaction catalysed by the enzymes of branched-chain amino acid metabolism, reductoisomerase and acetolactate decarboxylase

The alkali-catalysed rearrangement of (R)-[1-13C]-3-hydroxy-3-methylpentan-2-one has been studied. Rearrangement via a transition state having an anti arrangement of C–O bonds was preferred over that with a syn arrangement by a factor of 1.8:1. The result is of interest in relation to the mechanism of action of the enzymes reductoisomerase and acetolactate decarboxylase, both of which are involved in the metabolism of the branched-chain amino acids. The structure and relative configuration of the product 23 of bromolactonisation of N-methacrylolyl L-proline 22 were determined by X-ray crystallographic analysis.

N. Alcock | D. Crout | C. R. Mcintyre

[1] D. Crout,et al. Stereochemistry of Valine Biosynthesis , 1980 .

[2] K. Koga,et al. Asymmetric halolactonisation reaction—1 , 1979 .

[3] K. Koga,et al. Asymmetric halolactonisation reaction-2 , 1979 .

[4] Koji Nishihara,et al. Conformation of Methacryloyl-L-proline , 1973 .

[5] C. Stevens,et al. Hydroxy ketone rearrangements. II. Kinetics and mechanism of the thermal rearrangements of optically active .alpha.-hydroxy ketones. Example of a cyclic three-component equilibrium , 1973 .

[6] J. Dubois,et al. Metathetical transpositions of di-tert-alkyl ketones. Correlation of the structure with the migratory aptitudes of the methyl and ethyl groups , 1968 .

[7] J. Dubois,et al. Di-tert-alkyl ketone rearrangements. Structural environment influences on the migration of ethyl and methyl groups , 1968 .

[8] R. P. Mayer,et al. Rearrangement of Alkyl Groups. Kinetic and Tracer Studies in the Pinacol Rearrangement1 , 1959 .

[9] G. W. Stacy,et al. Cortical Steroid Analogs. II. The Synthesis of Open-chain Dihydroxyacetones from 2,3-Butanedione1 , 1957 .

[10] O. Neville. C14 tracer studies in the rearrangements of unsymmetrical alpha-diketones; phenylglyoxal to mandelic acid. , 1948, Journal of the American Chemical Society.