An efficient catalytic three‐step synthesis of enantiopure triacylglycerols

Abstract

With the developments in high performance chromatography and mass spectrometry, the analysis of complex mixtures of closely related triacylglycerols has come within reach. Currently, however, the availability of chemically pure triacylglycerols is limited, mainly due to the lack of efficient synthetic methods that allow their synthesis. Here, we report an efficient and operationally simple three‐step synthesis of enantiopure triacylglycerols with yields ranging from 79 to 92%, that tolerates a broad range of saturated and unsaturated fatty acids. Furthermore, we developed an automated protocol, which might greatly facilitate the synthesis of triacylglycerol libraries. Practical applications: The analysis of the composition of milk fat and as analytical standards in lipidomics. An efficient three‐step synthesis of enantiopure triacylglycerols with yields ranging from 79 to 92% is reported. This is accompanied by an automated protocol for triacylglycerol synthesis.

Synthesis of acylglycerol derivatives by mechanochemistry

“…This, assumption was confirmed by analysis of the sample by high-performance liquid chromatography-chiral stationary phase (CSP-HPLC, for more details, see Supporting Information File 1). Access to enantiopure MAGs could be achieved under similar reaction conditions by starting from optically active commercially available silyl-protected glycidol derivatives [27,43].…”

Conjugates of 1,3‐ and 1,2‐Acylglycerols with Stigmasterol: Synthesis, NMR Characterization, and Impact on Lipid Bilayers

“…Contrary to the synthesis of acylglycerols with stigmasterol moiety at internal position, the synthetic strategy to obtain their counterparts from III and IV groups involved firstly the attachment of the stigmasterol residue to glycerol backbone followed by the introduction of fatty acid residues (Scheme 2). The starting substrate was commercially available (S)-solketal (11) which has been widely used in the synthesis of acylglycerols [45][46][47][48] or glycerophospholipids. [49] In the case of triacylglycerol synthesis typical procedure involved esterification of free primary hydroxy group, opening of acetal ring and subsequent esterification of released diol with two molecules of appropiate fatty acid.…”

Synthesis of phosphatidic acids via cobalt(salen) catalyzed epoxide ring-opening with dibenzyl phosphate

“…It was shown later that this cobalt catalyzed epoxide-opening esterification could also be used for the synthesis of enantiopure triacylglycerols. 23 As illustrated, the synthesis of phosphatidic acids has seen significant improvements over the years, but the routes still are quite laborious and rely on moisture-sensitive phosphoramidite coupling reactions. To improve on these strategies, a switch from a trivalent phosphorus source to a pentavalent phosphorus source would be advantageous.…”

“…It was shown later that this cobalt catalyzed epoxide-opening esterification could also be used for the synthesis of enantiopure triacylglycerols. 23 …”