Glycolipids synthesis: improved hydrazinolysis conditions for preparation of 1,2-polyunsaturated fatty acyl-β-monogalactosyl-glycerols

Pagano, Dario; Cutignano, Adele; Manzo, Emiliano; Tinto, Francesco; Fontana, Angelo

doi:10.1016/j.carres.2016.02.005

Cited by 10 publications

(14 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Further in the synthesis, they were replaced by a levulinyl ester. On the one hand, acetate groups preserve the advantage of stereoselectivity in the formation of the β-glycosidic bond by anchimeric assistance [ 15 , 16 ], but, on the other hand, levulinic acid is more completely and selectively removable by hydrazine under mild acetate-buffered conditions, which is pushed by the formation of 6-keto-3-methyl-1,4,5,6-tetrahydro-pyridazine as a by-product [ 17 ]. As shown in Scheme 1 , the synthesis begins with the acetylation of d -glucose.…”

Section: Resultsmentioning

confidence: 99%

An Alternative Approach for the Synthesis of Sulfoquinovosyldiacylglycerol

et al. 2021

View full text Add to dashboard Cite

Sulfoquinovosyldiacylglycerol (SQDG) is a glycolipid ubiquitously found in photosynthetically active organisms. It has attracted much attention in recent years due to its biological activities. Similarly, the increasing demand for vegan and functional foods has led to a growing interest in micronutrients such as sulfolipids and their physiological influence on human health. To study this influence, reference materials are needed for developing new analytical methods and providing enough material for model studies on the biological activity. However, the availability of these materials is limited by the difficulty to isolate and purify sulfolipids from natural sources and the unavailability of chemical standards on the market. Consequently, an alternative synthetic route for the comprehensive preparation of sulfolipids was established. Here, the synthesis of a sulfolipid with two identical saturated fatty acids is described exemplarily. The method opens possibilities for the preparation of a diverse range of interesting derivatives with different saturated and unsaturated fatty acids.

show abstract

Section: Resultsmentioning

confidence: 99%

An Alternative Approach for the Synthesis of Sulfoquinovosyldiacylglycerol

et al. 2021

View full text Add to dashboard Cite

show abstract

“…For these reasons, we decided to explore the use of acetate as transient protecting group for the hydroxy functions of the sugar moiety. The acetoxy derivatives are stable under a wide range of conditions and, most importantly, the presence of the acetate residue at C-2′ is capable of ensuring an excellent stereoselectivity in the formation of the β glycosidic bond by anchimeric assistance [ 23 , 24 ]. On the other hand, acetate removal implies basic conditions that are not suitable for preserving the ester linkage of glycerol with the acyl chains.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, acetate removal implies basic conditions that are not suitable for preserving the ester linkage of glycerol with the acyl chains. To this end, a careful tuning of hydrolysis by hydrazine was crucial to completing the synthesis of the sulfolipid [ 23 , 24 ].…”

Section: Resultsmentioning

confidence: 99%

“…At this point, with the aim of introducing the sulfonic function on carbon 6′, a selective removal of sugar acetyl groups without affecting the acyls on glycerol was necessary to obtain β-glucosyl-distearoyl-glycerol 8 . This was achieved by an accurate setting of the basic conditions that drove us to use monohydrate hydrazine in an amount of 2.4 moles per acetate unit at a temperature below 45 °C [ 23 , 24 ]. After trytilation of the primary alcohol of glucose (compound 9 , 70 %), acetylation (compound 10 , 89%), detrytilation [ 28 ] (compound 11 , 82%) and subsequent introduction on C-6′ of the tosyl function (compound 12 , 80%) permitted the insertion of a thioacetate group (compound 13 , 93%) [ 29 ].…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Chemical Synthesis of Marine-Derived Sulfoglycolipids, a New Class of Molecular Adjuvants

et al. 2017

Self Cite

View full text Add to dashboard Cite

Vaccines play a primary role in the protection of human health by preventing infectious and chronic diseases. Recently we have reported 1,2-O-distearoyl-3-O-β-d-sulfoquinovosylglycerol (β-SQDG18), here named Sulfavant A (1), which shows promising properties as a new molecular adjuvant in in vitro and in vivo tests. In the present manuscript, we provide full details about a synthetic strategy for the preparation of 1, including a discussion of chemical determinants of the activity and the major technical hurdles we faced during the study. Synthesis of Sulfavant A (1) is achieved by a versatile procedure based on a trichloroacetimidate methodology and peracetate sugar precursors. The final design opens possibilities for the preparation of a series of interesting analogs for further pharmacological optimization and development, including derivatives containing different saturated and polyunsaturated fatty acids (e.g., 17 and 22).

show abstract

“…122 After their work, Manzo et al 123 showed that acetate is suitable for the synthesis of a wide range of MGDG, allowing for incorporation of saturated and unsaturated fatty acids. Pagano et al 124 developed a milder and selective protocol to deacetylation of the protected hydroxyls on galactose and kept the unsaturated fatty acyl group linked to a glycerol backbone. In general, there are some obvious drawbacks of chemical synthesis methods, such as multiple synthesis steps and the inevitable use of toxic substances during the synthesis process.…”

Section: ■ Synthesis Of Structured Mgdg and Dgdgmentioning

confidence: 99%

Galactosyldiacylglycerols: From a Photosynthesis-Associated Apparatus to Structure-Defined In Vitro Assembling

Lyu

Gao

Guo

2021

J. Agric. Food Chem.

View full text Add to dashboard Cite

Being ubiquitously present in plants, microalgae, and cyanobacteria and as the major constituents of thylakoid membranes, monogalactosyldiacylglycerol (MGDG) and digalactosyldiacylglycerol (DGDG) make up approximately 52 and 26%, respectively, of chloroplast lipids. Thylakoid membranes harbor the photosynthetic complexes and numerous essential biochemical pathways where MGDG and DGDG play a central role in facilitating photosynthesis light reaction, maintaining chloroplast morphology, and responding to abiotic stresses. Furthermore, these galactolipids are also bioactive compounds with antitumor, antimicrobial, antiviral, immunosuppressive, and anti-inflammatory activities and important nutritional value. These characteristics are strictly dependent upon their fatty acyl chain length, olefinic nature, and stereoconfiguration. However, their application potentials are practically untapped, largely as a result of the fact that their availability in large quantity and high purity (structured galactolipids) is challenging. In addition to laborious extraction from natural sources, in vitro assembling of these molecules could be a promising alternative. Thus, this review updates the latest advances in elucidating biosynthesis paths of MGDG and DGDG and related enzyme systems, which present invaluable inspiration to design approaches for a retrosynthesis of galactolipids. More critically, this work summarizes recent developments in the biological and enzymatic syntheses of galactolipids, especially the strategic scenarios for the construction of in vitro enzymatic and/or chemoenzymatic synthesis routes. Protein engineering of enzymes involved in the synthesis of MGDG and DGDG to improve their properties is highlighted, and the applications of galactolipids in foods and medicine are also discussed.

show abstract

Glycolipids synthesis: improved hydrazinolysis conditions for preparation of 1,2-polyunsaturated fatty acyl-β-monogalactosyl-glycerols

Cited by 10 publications

References 38 publications

An Alternative Approach for the Synthesis of Sulfoquinovosyldiacylglycerol

An Alternative Approach for the Synthesis of Sulfoquinovosyldiacylglycerol

Chemical Synthesis of Marine-Derived Sulfoglycolipids, a New Class of Molecular Adjuvants

Galactosyldiacylglycerols: From a Photosynthesis-Associated Apparatus to Structure-Defined In Vitro Assembling

Contact Info

Product

Resources

About