An unexpected rearrangement of pent-4-enofuranosides to cyclopentanones upon hydrogenolysis of the anomeric benzyl group

Shenyou Nie; Xiaoping Chen; Yuyong Ma; Wei Li; Biao Yu

doi:10.1016/j.carres.2016.06.006

An unexpected rearrangement of pent-4-enofuranosides to cyclopentanones upon hydrogenolysis of the anomeric benzyl group

Carbohydr Res. 2016 Sep 2:432:36-40. doi: 10.1016/j.carres.2016.06.006. Epub 2016 Jun 18.

Authors

Shenyou Nie¹, Xiaoping Chen¹, Yuyong Ma¹, Wei Li², Biao Yu³

Affiliations

¹ State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
² State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China. Electronic address: lmwave@mail.sioc.ac.cn.
³ State Key Laboratory of Bio-organic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China. Electronic address: byu@mail.sioc.ac.cn.

PMID: 27366975
DOI: 10.1016/j.carres.2016.06.006

Abstract

During our synthesis toward the unique nucleoside antibiotic A201A, we were surprised to find that a benzyl arabino-pent-4-enofuranoside underwent a Ferrier II-like rearrangement readily to provide the corresponding cyclopentanone derivative in high yield and stereoselectivity upon hydrogenolysis of the anomeric benzyl group.

Keywords: Cyclopentanone; Exocyclic enol ether; Ferrier II rearrangement; Furanoside; Hydrogenolysis.

MeSH terms

Aminoglycosides / chemical synthesis*
Aminoglycosides / chemistry
Benzyl Compounds / chemistry
Cyclopentanes / chemistry*
Glycosides / chemistry*
Hydrogen / chemistry
Molecular Structure
Stereoisomerism

Substances

Aminoglycosides
Benzyl Compounds
Cyclopentanes
Glycosides
cyclopentanone
A 201A
Hydrogen