‘Chiron’ approach to stereoselective synthesis of sphinganine and unnatural safingol, an antineoplastic and antipsoriatic agent

Abstract

Highly stereoselective total syntheses of sphinganine 1 and antineoplastic and antipsoriatic drug safingol 17 have been demonstrated.

Organocatalytic Asymmetric Tandem α‐Aminooxylation–Henry Reactions for the Synthesis of 1,2‐Diols: Total Synthesis of (–)‐l‐threo‐Sphinganine

“…In a continuation of our ongoing research programme towards the asymmetric synthesis of biologically active compounds, we demonstrated the synthetic application of the developed tandem α‐aminooxylation–Henry reactions through the total synthesis of l ‐ threo ‐sphinganine ( 21 ) …”

“…Finally, concomitant reduction of ester and azide groups of derivative 28 with LiAlH 4 in THF at 70 °C gave the target l ‐ threo ‐sphinganine 21 in 81 % yield {[ α ] D 25 = –7.5 ( c = 0.09, C 2 H 5 OH); lit. [10a] –7.6 ( c = 0.09, C 2 H 5 OH)}.…”

“…[ α ] D 25 = –23.5 ( c = 0.5, CHCl 3 /MeOH, 3:1); [ α ] D 25 = –7.5 ( c = 0.09, C 2 H 5 OH) [lit. [10a] –7.6 ( c = 0.09, C 2 H 5 OH)]. IR (MeOH): ν̃ = 3623, 3425, 1565, 756 cm –1 .…”

Synthetic Strategies for Modified Glycosphingolipids and Their Design as Probes

“…The major challenges associated with the synthesis of sphingoid bases involve setting the erythro stereochemistry and, for sphingosine in particular, setting the trans stereochemistry of the alkene . In general, erythro stereochemistry has been achieved from stereochemical starting materials, such as l -serine − or carbohydrates, − or from racemic intermediates using various asymmetric strategies. − Synthetic methods to access sphingoid bases have been thoroughly reviewed elsewhere. − …”