Convenient stereocontrolled amidoglycosylation of alcohols with acetylated glycals and trichloroethoxysulfonamide. (3rd November 2016)

• Record Type: Journal Article
• Authors: Murakami, Teiichi; Sato, Yukari; Yoshioka, Kyoko; Tanaka, Mutsuo
• Is Part Of: Carbohydrate research. Volume 434(2016)
• Page Start: 121
• Page End: 131
• Publication Date: 2016-11-03
• Subjects: Glycals -- Amidoglycosylation -- Stereocontrol -- Aziridination -- Nitrene; OCHCTBFSNYEZLY-YRHVJKGHSA-N -- GAHCGPURGMYQMX-IZXZMTOFSA-N -- AMVGPJRGMBPDFR-CUQGBWDPSA-N; Tri-O-Acetyl-D-glucal (PubChem CID: 688303) -- Tri-O-Acetyl-D-galactal (PubChem CID: 640125) -- Hexa-O-Acetyl-lactal (PubChem CID: 2734746) -- Iodosobenzene (PubChem CID: 92125) -- 2, 2, 2-Trichloroethoxysulfonamide (PubChem CID: 3052707) -- ChloroBenzene (PubChem CID: 79645) -- 12-Bromo-1-dodecanol (PubChem CID: 137895); Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2016.09.001
• Languages: English
• ISSNs: 0008-6215

Abstract

Abstract: A regio- and stereo-controlled, rhodium(II)-catalyzed amidoglycosylation of alcohols has been developed using O -acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene. This one-pot amidoglycosylation was applied to a variety of primary and secondary alcohols to afford the β- O -glycosides with acceptable yields up to 84%. The reaction would proceed via stereoselective intermolecular aziridination of the glycal from the α-face followed by SN 2 reaction with alcohol at C-1 from the β-face to give 1, 2:2, 3-di- trans -substituted isomer only. Graphical abstract: Highlights: A regio-controlled one-pot synthesis of 2-deoxy-2-sulfonamino-1- O -glycosides from acetylated glycals. 1, 2:2, 3-Di- trans -substituted glycosides were formed in a stereospecific manner. This amidoglycosylation was applied to a variety of primary and secondary alcohols. The reaction would proceed via rhodium(II)-catalyzed intermolecular aziridination with a sulfonyl-nitrene.