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Tuning the Chemoselectivity of Silyl Protected Rhamnals by Temperature and Brønsted Acidity: Kinetically Controlled 1,2-Addition vs Thermodynamically Controlled Ferrier Rearrangement

Author:
Wang, Jincai, Deng, Chuqiao, Zhang, Qi, Chai, Yonghai
Source:
Organic letters 2019 v.21 no.4 pp. 1103-1107
ISSN:
1523-7052
Subject:
acidity, alcohols, catalysts, chemical structure, chemoselectivity, glycosylation, temperature, thermodynamics
Abstract:
An acidity- and temperature-dependent chemoselective glycosylation of silyl-protected rhamnals with alcohols has been revealed. The reaction undergoes a 1,2-addition pathway with (±)-CSA as the catalyst at rt, affording kinetically controlled 2-deoxyl rhamnosides. In contrast, only thermodynamically controlled 2,3-unsaturated rhamnosides are formed via Ferrier rearrangement when elevating reaction temperature to 85 °C or using CF₃SO₃H instead. This tunable glycosylation allows facile and practical access to both 2-deoxyl and 2,3-unsaturated rhamnosides with excellent yields and high α-stereoselectivity.
Agid:
6310504