Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion DOI Creative Commons
Hao Guo, Jan‐Lukas Kirchhoff, Carsten Strohmann

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(7)

Published: Dec. 20, 2023

Abstract Harnessing unconventional noncovalent interactions (NCIs) is emerging as a formidable synthetic approach in difficult‐to‐access glycosidic chemical space. C ‐Glycosylation, particular, has gained flurry of recent attention. However, most reported methods are restricted to the relatively facile access α‐ ‐glycosides. Herein, we disclose β‐stereoselective glycosylation indoles by employing phosphonoselenide catalyst. The robustness this protocol exemplified its amenability for reaction at both indolyl ‐ and N reactivity sites. In contrast previous reports, which chalcogens were solely involved Lewis acidic activation, our mechanistic investigation unraveled that often neglected flanking aromatic substituents phosphonoselenides can substantially contribute catalysis engaging π‐interactions. Computations NMR spectroscopy indicated chalcogenic components catalyst be collectively exploited foster conformational distortion glycal away from usual half‐chair boat conformation, liberates convex β‐face nucleophilic attack.

Language: Английский

Regio- and Stereo-selective Synthesis of 1β-/3R-Aryl Thiosugar DOI Open Access

Fakai Zou,

Nengzhong Wang, Hui Yao

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(2), P. 593 - 593

Published: Jan. 1, 2024

Language: Английский

Citations

1
Thiazolylketol Acetates as Glycosyl Donors: Stereoselective Synthesis of a C-Ketoside DOI Creative Commons
Clark Ferrari,

Alessandro Dondoni,

Alberto Marra

et al.

Molbank, Journal Year: 2024, Volume and Issue: 2024(3), P. M1883 - M1883

Published: Sept. 23, 2024

We have already proven that thiazolylketol acetates, synthetised by addition of 2-lithiothiazole to sugar lactones followed acetylation, are efficient glycosyl donors in the presence O-, N-, and P-nucleophiles. describe here their first use C-glycosidation using trimetylsilyl cyanide as acceptor order prepare, after thiazole-to-formyl unmasking reduction, corresponding C-ketosides.

Language: Английский

Citations

1
Synthesis of C-glycosides enabled by palladium-catalyzed glycosylation reactions DOI

Wenli Tong,

Jie‐Ping Wan, Jianchao Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(23), P. 6918 - 6941

Published: Jan. 1, 2024

This review highlights the recent progress in palladium-catalyzed C -glycosylation reactions for synthesis of -glycosides.

Language: Английский

Citations

1
C‐Aryl Glycosylation via Interrupted Pummerer Rearrangement† DOI
Jiagen Li, Xuefeng Jiang

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(21), P. 2843 - 2847

Published: July 6, 2023

Comprehensive Summary C ‐aryl glycosides are an important kind of carbohydrate derivatives for drug discovery, due to their distinctive attributes resistance hydrolysis from enzymes. Herein, glycosylation was established the synthesis 2‐sulfur glycals and 1,2‐dihydrobenzofuran‐fused via interrupted Pummerer process, featured with sulfonium‐tethered [3,3]‐sigmatropic rearrangement between sulfoxide phenols. This protocol offers a broad substrate scope diverse glycosyl Dapagliflozin, Empagliflozin, Ipragliflozin analogs were straightforward achieved, respectively.

Language: Английский

Citations

3
Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion DOI Creative Commons
Hao Guo, Jan‐Lukas Kirchhoff, Carsten Strohmann

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(7)

Published: Dec. 20, 2023

Abstract Harnessing unconventional noncovalent interactions (NCIs) is emerging as a formidable synthetic approach in difficult‐to‐access glycosidic chemical space. C ‐Glycosylation, particular, has gained flurry of recent attention. However, most reported methods are restricted to the relatively facile access α‐ ‐glycosides. Herein, we disclose β‐stereoselective glycosylation indoles by employing phosphonoselenide catalyst. The robustness this protocol exemplified its amenability for reaction at both indolyl ‐ and N reactivity sites. In contrast previous reports, which chalcogens were solely involved Lewis acidic activation, our mechanistic investigation unraveled that often neglected flanking aromatic substituents phosphonoselenides can substantially contribute catalysis engaging π‐interactions. Computations NMR spectroscopy indicated chalcogenic components catalyst be collectively exploited foster conformational distortion glycal away from usual half‐chair boat conformation, liberates convex β‐face nucleophilic attack.

Language: Английский

Citations

2