The first examples of iminosugar-type 2-deoxy(thio)glycoside mimetics are reported. The key step is the acti-vation of a bicyclic iminoglycal carbamate to generate a highly reactive acyliminium cation. Cerium(IV) am-monium nitrate efficiently promoted the formation of 2-deoxy S-glycosides in the presence of thiols, probably by in situ generation of catalytic HNO3, with complete α-stereoselectivity. Cooperative phosphoric ac-id/Schreiner's thiourea organocatalysis proved better suited for generating 2-deoxy O-glycosides, significantly broadening the scope of the approach.
Stereoselective Synthesis of Iminosugar 2-Deoxy(thio)glycosides from Bicyclic Iminoglycal Carbamates Promoted by Cerium(IV) Ammonium Nitrate and Cooperative Brønsted Acid-Type Organocatalysis / Cristina Nativi. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - STAMPA. - (2020), pp. 5038-5047.
Stereoselective Synthesis of Iminosugar 2-Deoxy(thio)glycosides from Bicyclic Iminoglycal Carbamates Promoted by Cerium(IV) Ammonium Nitrate and Cooperative Brønsted Acid-Type Organocatalysis
Cristina Nativi
2020
Abstract
The first examples of iminosugar-type 2-deoxy(thio)glycoside mimetics are reported. The key step is the acti-vation of a bicyclic iminoglycal carbamate to generate a highly reactive acyliminium cation. Cerium(IV) am-monium nitrate efficiently promoted the formation of 2-deoxy S-glycosides in the presence of thiols, probably by in situ generation of catalytic HNO3, with complete α-stereoselectivity. Cooperative phosphoric ac-id/Schreiner's thiourea organocatalysis proved better suited for generating 2-deoxy O-glycosides, significantly broadening the scope of the approach.
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