Modular Synthesis of Aryl Thio/Selenoglycosides via the Catellani Strategy

Abstract

We described a novel palladium-catalyzed domino procedure for the preparation of (hetero)­aryl thio/selenoglycosides. Readily available (hetero)­aryl iodides and easily accessible 1-thiosugars/1-selenosugars are utilized as the substrates. Meanwhile, 10 types of sugars are quite compatible with this reaction with good regio- and stereoselectivity, high efficiency, and broad applicability (up to 89%, 53 examples). This method enables the straightforward formation of the C­(sp2)–S/Se bond of (hetero)­aryl thio/selenoglycosides.

Atom-Economic Synthesis of Unsymmetrical gem-Diarylmethylthio/Seleno Glycosides via Base Mediated C(O)–S/Se Bond Cleavage and Acyl Transfer Approach of Glycosylthio/Selenoacetates

“…Also, Messaoudi and co-workers established a PdG3 XantPhos-catalyzed coupling reaction of an in situ generated anomeric selenolate anion from β- p -methylbenzoyl selenoglycoside with aryl/alkenyl iodides for synthesizing selenoglycosides (Scheme b). In 2021, the Liang group first developed palladium/norbornene cooperative catalyzed ortho -acylation and ipso -thio/selenolation for the synthesis of aryl S/Se-glycosides via the Catellani Strategy (Scheme c). The green process involving both the glycosylthio/seleno group and acyl group to incorporate into another moiety in an atom economical manner to avoid the generation of waste has remained elusive .…”

“…In 2021, the Liang group first developed palladium/norbornene cooperative catalyzed ortho -acylation and ipso -thio/selenolation for the synthesis of aryl S/Se-glycosides via the Catellani Strategy (Scheme c). The green process involving both the glycosylthio/seleno group and acyl group to incorporate into another moiety in an atom economical manner to avoid the generation of waste has remained elusive . However, the cross-coupling protocol or Modular synthesis approach demands reaction conditions such as high catalyst loadings (30 mol % in the case of Ni catalysis), specialized phosphine ligands for the Pd catalysis, elevated reaction temperatures (80–120 °C cases of Pd or Cu catalysis), and long reaction times which often limit the practicability or the scope of substrates.…”

CuMoO4 Catalyzed Csp2−Se Cross‐Coupling of Aryl Bromide and Iodide with Diaryldiselenides in Water

“…However, NaOH and KO t Bu provided only 10-15 % of yield in water solvent under standard condition (Table 1, entry 10-12). Standardizing temperature revealed that there is no product formation below 70 °C in water solvent (Table 1, entry [14][15].…”

Metal-free photocleavage of the C(non-acyl)–S bond of thioesters for regioselective pyridylthioesterification of styrenes

“…Transition metal-catalyzed transformation of thioesters via C(O)–S bond cleavage is a promising synthetic route to construct C–C and C–heteroatom bonds (Scheme 1a). 12 Thioesters have also been used as bifunctional agents in Pd-, Pt-, and Rh-catalyzed thioacylation or decarbonylative carbothiolation of alkynes, 13 allene, 14 diazos, 15 aryl halides, 16 and 2-naphthylamine. 17 The difunctionalization of alkenes with thioesters remains largely unexplored (Scheme 1b).…”