Controllable Activation of Pd‐G3 Palladacycle Precatalyst in the Presence of Thiosugars: Rapid Access to 1‐Aminobiphenyl Thioglycoside Atropoisomers at Room Temperature

Abstract

A controllable method for the functionalization of XantPhos Pd-G3 precatalyst with thiosugars and thiols has been established. Under mild and operationally simple reaction conditions through just mixing of precatalyst and thiosugars (α- or β-mono-, di- and poly-thiosugar derivatives) in water at 25 °C for 20 min, a series of 1-aminobiphenyl thioglycosides that are difficult to synthesize by classical methods has been synthesized in very high yields.

Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

“…In continuation of the works on arylation of thiosugars, 1-aminobiphenyl was introduced by using the corresponding cyclopalladate in water at room temperature (Scheme , A) …”

“…In continuation of the works on arylation of thiosugars, 1aminobiphenyl was introduced by using the corresponding cyclopalladate 172 in water at room temperature (Scheme 15, A). 173 The authors used the same complex as a catalyst for the synthesis of S-linked saccharides and S-linked glycoconjugates. 174 This group also studied a tandem three-component Scross-coupling reaction and the Suzuki reaction producing unsymmetrical biaryl thioglycosides (Scheme 15, B).…”

Synthesis of axially chiral biaryl thioglycosides through thiosugar-directed Pd-catalyzed asymmetric C–H activation

“…Indeed, thiosugars can be used as glycomimetic being much more stable to both chemical and enzymatic degradation. In this context, we reported recently two approaches towards a wide range of biaryl thioglycosides 6 via (i) the activation of a Pd-G 3 -catalyst with various glycosyl thiols 12 and (ii) the one pot multicomponent coupling of dihalogenated arenes with thiosugars and boronic acids.…”

One-Pot Assembly of Unsymmetrical Biaryl Thioglycosides through Chemoselective Palladium-Catalyzed Three-Component Tandem Reaction

“…16 Nevertheless, structures of biaryls bearing thiosugars and synthetic methods leading to their formation are non-existent. 17 Thiosugars can be used as sugar surrogates; therefore, their introduction into biaryls is highly relevant since biarylthioglycosides can be investigated as mimetics of biologically relevant O-glycosides. S-Glycosides are much more stable than O-glycosides to both chemical and enzymatic degradation and have been utilized as enzyme inhibitors in various biochemical studies.…”

“…Among these are the Diels–Alder cycloaddition or the reaction of aryl halides with bis­(pinacolato)­diboron followed by coupling with another aryl halide . Nevertheless, structures of biaryls bearing thiosugars and synthetic methods leading to their formation are nonexistent …”