Stereochemistry of the Glutamate Mutase Reaction
M. Sprecher 1, R. L. Switzer 1, and David B. Sprinson 1
From the
1 From the Departments of Biochemistry, College of Physicians and Surgeons, Columbia University, New York, New York 10032, and University of California, Berkeley, California
4-Deuterioglutamic acid was prepared by incubation in D2O of ammonium mesaconate with an extract of Clostridium tetanomorphum. In these extracts, methylaspartase catalyzed the formation of threo-3-methyl-l-aspartate-3-D, which was then rearranged to glutamate by the cobamide coenzyme-dependent glutamate mutase. The monodeuteriosuccinate obtained by chloramine-T oxidation of the glutamate showed a plain negative optical rotatory dispersion curve, and was therefore (R)-succinate-2-D. It was concluded that the intramolecular rearrangement of thero-3-methyl-l-aspartate to l-glutamate proceeded by net inversion of configuration of carbon atom 3. (R)-Succinate-2-D was also prepared from (2S,3R)-aspartic acid-3-D.
Submitted on July 9, 1965