TIPS group-assisted isomerization of benzyl protected d-manno- and d-glucopyranose to d-fructofuranose derivatives

Maxim Y Karpenko; Polina I Abronina; Alexander I Zinin; Alexander O Chizhov; Leonid O Kononov

doi:10.1016/j.carres.2023.108942

TIPS group-assisted isomerization of benzyl protected d-manno- and d-glucopyranose to d-fructofuranose derivatives

Carbohydr Res. 2023 Dec:534:108942. doi: 10.1016/j.carres.2023.108942. Epub 2023 Sep 21.

Authors

Maxim Y Karpenko¹, Polina I Abronina², Alexander I Zinin¹, Alexander O Chizhov¹, Leonid O Kononov³

Affiliations

¹ N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Leninsky Prosp. 47, 119991, Moscow, Russian Federation.
² N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Leninsky Prosp. 47, 119991, Moscow, Russian Federation. Electronic address: polina-abronina@yandex.ru.
³ N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, Leninsky Prosp. 47, 119991, Moscow, Russian Federation. Electronic address: leonid.kononov@gmail.com.

PMID: 37769375
DOI: 10.1016/j.carres.2023.108942

Abstract

Base-promoted (MeONa in MeOH or imidazole in DMF) isomerization of a series of 3,4,6-tri-O-benzyl-d-gluco- and d-mannopyranose derivatives with triisopropylsilyl (TIPS) substituents was studied. The presence of a bulky TIPS group at O-1 or O-2 was shown to be favorable for the isomerization of benzyl protected d-gluco- and d-mannopyranose derivatives to d-fructofuranose derivatives, in which the bulky silyl group occupies less sterically hindered primary position. The highest yield (33%) of the fructofuranose derivative was achieved when 3,4,6-tri-O-benzyl-2-O-triisopropylsilyl-d-mannopyranose was treated with MeONa in MeON at 50 °C.

Keywords: Isomerization; Triisopropylsilyl group; d-fructofuranose; d-glucopyranose; d-mannopyranose.

MeSH terms

Isomerism
Mannose*

Substances

Mannose