Approaches to polyunsaturated sphingolipids: new conformationally restrained analogs with minimal structural modifications

作者：Nieves Ingrid; Abad Jose Luis; Ruth Montes L; Goni Felix M; Delgado Antonio^*

来源：Tetrahedron, 2016, 72(5): 605-612.

DOI：10.1016/j.tet.2015.11.067

• Sphingolipids
• Diastereoselectivity
• Polyene
• Hydrozirconation
• Ceramide
• Sphingosine

Conformationally restrained sphingolipids 1-4, arising from the introduction of a polyene or a polyenyne moiety as part of the sphingoid backbone, have been synthesized. While addition of polyene acetylides 6 and 7 to Garner's aldehyde afforded the corresponding Felkin-Anh anti -addition adducts, addition of alkenylzirconocenes showed no diastereoselectivity. This behaviour was also observed from protected serinal 14, which allowed the synthesis of the acid-sensitive pentaene sphingosine backbone present in ceramide 4. Despite the inherent limitations of the synthetic approaches here reported, their application to such highly conjugated polyene sphingoid analogs is unprecedented.

• 出版日期2016-2-4