Synthesis and revised stereochemical assignment of C -allyl glucopyranosides and derivatives

Cyanine-based [18F]F-C-glycosyl dual imaging probe: synthesis, physico-chemical characterization, in vitro binding evaluation and direct [18F]fluorination

“…Compounds 1 , 21 2 , 22 3 , 22 and 11 34 were prepared according to previously described methods (see the ESI†).…”

“…25,26 Based on our expertise in the synthesis of such derivatives, we chose to introduce 18/19 F on the primary hydroxyl via nucleophilic substitution. [21][22][23][24] The cyanine was also regioselectively introduced thanks to a thoughtful protection/deprotection strategy. The pseudo-anomeric position was derivatized with an azido spacer allowing the late stage coupling of a vector via an efficient click reaction, the Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC).…”

“…27,28 First, tetra-O-Bn-derivative 1 was prepared from commercial 1-O-acetyl-2,3,4,6-tetra-O-benzyl-D-glucopyranose by insertion of an allyl group followed by hydroboration and bromination of the resulting alkene moiety, according to a known method. 21 We have recently described the synthesis of compound 3 22 starting from compound 1 (Scheme 1). Briefly, catalytic hydrogenolysis gave the fully deprotected derivative, which subsequently reacted with NaN 3 to afford the azido derivative.…”

“…The choice of the platform was guided by our expertise in carbohydrate chemistry and previous results demonstrating the efficient 18 F-fluorination of a C-glucosyl derivative on the primary hydroxyl. [21][22][23][24] Carbohydrates have never been used as a platform for this application and they are precisely convenient candidates due to their polyfunctional structure enabling a selective introduction of different entities at selected positions. The coupling of the C-glycosyl dual imaging probe was then illustrated with a model vector i.e.…”

Synthesis of anti-proliferative [3.3.0]furofuranone derivatives by lactonization and functionalization of C-glycosyl compounds

“…Close analogs of O-glycosyl derivatives, C-glycosyl compounds display chemical and biological stabilities toward enzymatic hydrolysis and are thus extensively studied. [1][2][3][4] In this context, our lab was early involved in the development of C-glycosidic derivatives [5][6][7][8] to build bioactive compounds, [9,10] peptidomimetic derivatives [11] suitable for imaging applications [12] and also for the design and synthesis of foldamers. [13,14] In the course of the synthesis of glycopeptides based on sugar γ-amino acids, we reported the spontaneous formation of a C-glycosyl bicyclic lactone in which the lactone ring is annulated to a furanoid system.…”