The intramolecular stabilizing effects of O-benzoyl substituents as a driving force of the acid-promoted pyranoside-into-furanoside rearrangement

• Alexey G. Gerbst,
• Sofya P. Nikogosova,
• Darya A. Rastrepaeva,
• Dmitry A. Argunov,
• Vadim B. Krylov and
• Nikolay E. Nifantiev

Beilstein J. Org. Chem. 2025, 21, 2456–2464, doi:10.3762/bjoc.21.187

• equilibrium lie outside the carbohydrate ring system. Consideration of such effects is essential to rationalize the reactivity of structurally complex and densely protected carbohydrate compounds. Keywords: benzoylated galactofuranosides; DFT; DLPNO-CCSD(T); pyranoside-into-furanoside rearrangement

Influence of per-O-sulfation upon the conformational behaviour of common furanosides

• Alexey G. Gerbst,
• Vadim B. Krylov,
• Dmitry A. Argunov,
• Maksim I. Petruk,
• Arsenii S. Solovev,
• Andrey S. Dmitrenok and
• Nikolay E. Nifantiev

Beilstein J. Org. Chem. 2019, 15, 685–694, doi:10.3762/bjoc.15.63

• . Lomonosov Moscow State University, Moscow, 119991, Russia 10.3762/bjoc.15.63 Abstract The studies on the recently discovered pyranoside-into-furanoside rearrangement have led us to conformational investigations of furanosides upon their total sulfation. Experimental NMR data showed that in some cases

• torsion angles [10]. The knowledge of conformational changes occurring in sulfated furanosides may be important for better understanding of the driving force of the pyranoside-into-furanoside rearrangement [14][15][16], which is widely used for preparative synthesis of different oligosaccharides

• analogous reactions (Scheme 1). The use of the n-propyl group as an aglycon allowed for efficient purification of the desired glycosides utilizing C18 reversed-phase chromatography. Galactofuranoside 3 was previously synthesized using pyranoside-into-furanoside rearrangement [14]. The per-O-sulfation [24