Straightforward synthesis of thiodisaccharides by ring-opening of sugar epoxides

The Journal of Organic Chemistry
Verónica E ManzanoOscar Varela

Abstract

3,4-Anhydro hexopyranosides have been prepared by diastereoselective epoxidation of derivatives of 2-propyl 3,4-dideoxy-alpha-D-erythro-hex-3-enopyranoside (5), selectively protected at HO-2 and HO-6. The allylic group at C-2, in 5 and derivatives, plays a critical role in the facial selectivity of the epoxidation reaction. Thus, the free HO-2 in 3 (the 6-O-acetyl derivative of 5) directs the attack of m-chloroperbenzoic acid from the more hindered alpha face of the molecule to give 2-propyl 6-O-acetyl-3,4-anhydro-alpha-D-allopyranoside (7) accompanied by the beta epoxide 6 as a very minor product. Reverse diastereoselectivity has been obtained when the HO-2 in 3 was substituted by a bulky tert-butyldimethylsilyl (TBS) group. In this case, the major isomer was the 2-O-TBS derivative of 6 (alpha-D-galacto configuration). The ring-opening of sugar epoxides by nucleophilic per-O-acetyl-1-thio-beta-D-glucopyranose (11) was employed as a convenient approach to the synthesis of (1-->3)- and (1-->4)-thiodisaccharides. For example, ring-opening of the oxirane 7 by 11 led to the expected regioisomeric per-O-acetyl thiodisaccharides beta-D-Glc-S-(1-->3)-4-thio-alpha-D-Glc-O-iPr (12) and beta-D-Glc-S-(1-->4)-4-thio-alpha-D-Gul-O-iPr (13)....Continue Reading

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Citations

Nov 19, 2011·The Journal of Organic Chemistry·Evangelina RepettoOscar Varela
May 16, 2014·The Journal of Organic Chemistry·Guillermo A Oliveira UdryOscar Varela
May 7, 2014·The Journal of Organic Chemistry·Panuwat PadungrosAlexander Wei
Apr 9, 2017·Bioorganic & Medicinal Chemistry·Alice TamburriniAnna Bernardi
Aug 8, 2014·Organic & Biomolecular Chemistry·Huali Wang, Xiangming Zhu
Nov 28, 2013·Chemistry, an Asian Journal·Alicia Megia-FernandezFrancisco Santoyo-Gonzalez
Jan 7, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alejandro E Cristófalo, María Laura Uhrig

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