Stereoselective synthesis of L‐[2,3,4,5‐D₄] ornithine

Abstract

SummarySynthesis of l- [2,3,4,5-D 4 ]ornithine in which all of the diastereotopic hydrogens were stereoselectively labeled with deuterium was investigated. The chirally deuterated 3-aminopropanal derivative, a key intermediate in this synthesis, was prepared by a catalytic deuteration of an unsaturated g-lactone derived for l-glutamic acid followed by several functional group interconversions. Condensation of the obtained deuterium-labeled 3-aminopropanal derivative with a chiral glycine template afforded unsaturated ornithine. The dehydroornithine was then subjected to a catalytic deuteration followed by deprotection to give the l-[2,3,4,5-D 4 ]ornithine.

Recent Developments for the Deuterium and Tritium Labeling of Organic Molecules

“…In analogy to what was mentioned above in the context of dehalogenative deuteration, the older technique using a heterogeneous palladium catalyst such as palladium on charcoal along with deuterium gas remains in use for the reductive deuteration of olefins (and alkynes) as well. − A recent example is shown in Scheme d . However, as the modern techniques can enable enantioselective or stereoselective reduction and are not as sensitive to the presence of labile protons (please note that the conditions in Scheme a even allow for the use of nondeuterated acetic acid), they represent a clear advantage.…”

Synthesis of Optically Active Deuterated Primary Amines via Reduction of N-tert-Butanesulfinyl Aldimines

“…During such efforts, we have found that o -ClPhCH­DNH 2 can be efficiently synthesized from the corresponding chiral N - tert -butanesulfinyl aldimines via reduction with N -Selectride and subsequent alcoholysis (Scheme ) . Considering the potential usefulness of deuterated chiral primary amines for the study of other reaction mechanisms, − we further investigated the reaction scope of this process. Herein, we wish to report our studies on this subject.…”