Efficient synthesis of deuterium- and tritium-labeledd-erythro-sphingosine

Abstract

Deuterium‐ and tritium‐labeled d‐erythro‐sphingosine (1b and 1c) were prepared by an efficient approach based on a known stereoselective total synthesis. Tritium was introduced at C−1 by [3H]NaBH4 reduction in the final synthetic step to give 1c of high radiochemical purity. 1,1,3‐Trideuterio‐d‐erythro‐sphingosine (1b) was prepared similarly and showed >99·5% enantiomeric purity and a high level of deuterium incorporation. Copyright © 1999 John Wiley & Sons, Ltd.

Absolute Configuration of the α,ω-Bifunctionalized Sphingolipid Leucettamol A from Leucetta microrhaphis by Deconvoluted Exciton Coupled CD

“…For example, the magnitudes of [α] D increase by two to three fold upon acetylation or benzoylation of sphingosine 20. Discrimination of threo from erythro isomers of sphingosine by 1 H NMR has been demonstrated with the corresponding Mosher’s acid derivatives which are also useful for estimating optical purities of sphingosine samples containing as little as 1% of the minor enantiomer 21. Nevertheless, errors of assignment in configuration of even simple monomeric marine aminoalcohols have been made and sole reliance upon some methods may be risky.…”

Stereoselective synthesis of (2S,3S,4Z)-4-fluoro-1,3-dihydroxy-2-(octadecanoylamino)octadec-4-ene, [(Z)-4-fluoroceramide], and its phase behavior at the air/water interface

“…The latter building block has already been used for the preparation of several γ-fluoro-α-amino acids [ 31 ]. This methodology, utilizing the corresponding ethyl iminoglycinate instead of 4 , was previously applied for the synthesis of natural D- erythro -sphingosine ( 1a ) [ 32 ], deuterium and tritium labeled sphingosines [ 33 ] and various other non-fluorinated sphingosine, sphinganine and phytosphingosine derivatives [ 34 ].…”

Preparation of Enantiomerically Pure Compounds Labeled with Isotopes of Hydrogen and Carbon

“…The titanium enolate, generated by treatment with ClTi(OEt) 3 in the presence of triethylamine, reacts with aldehydes to give (2R,3R)-and (2S,3S)-b-hydroxy-a-amino acyl derivatives, which upon hydrolytic cleavage of the auxiliary furnish the free acids of the allo-threonine type in excellent stereoselectivities ( > 98% e.e.) Use of NaB 3 H 4 as a reducing agent afforded the respective [1,1-3 H 2 ,3-2 H]analog 152 . As illustrated in Figure 11.77, application of this strategy to (2E)-2-[1-2 H]hexadecenal (225) furnished the (2R,3R)-adduct 226 in 70% yield after MPLC separation.…”