Wu, Jicheng; Li, Xiaolei; Qi, Xiaotian; Duan, Xiyan; Cracraft, Weston L.; Guzei, Ilia A.; Liu, Peng; Tang, Weiping published the artcile< Site-Selective and Stereoselective O-Alkylation of Glycosides by Rh(II)-Catalyzed Carbenoid Insertion>, Application In Synthesis of 4064-06-6, the main research area is transition state crystal structure glycoside preparation disaccharide; crystal structure glycoside preparation stereoselective glycosylation catalyst disaccharide; rhodium catalyzed regioselective stereoselective glycosylation alkylation glycoside preparation DFT; regioselective stereoselective glycosylation protecting group alkylation glycoside carbenoid catalyzed.
Carbohydrates are synthetically challenging mols. with vital biol. roles in all living systems. Selective synthesis and functionalization of carbohydrates provide tremendous opportunities to improve our understanding on the biol. functions of this fundamentally important class of mols. However, selective functionalization of seemingly identical hydroxyl groups in carbohydrates remains a long-standing challenge in chem. synthesis. We herein describe a practical and predictable method for the site- and stereoselective alkylation of carbohydrate hydroxyl groups via Rh(II)-catalyzed insertion of metal carbenoid intermediates. This represents one of the mildest alkylation methods for the systematic modification of carbohydrates. D. functional theory (DFT) calculations suggest that the site-selectivity is determined in the Rh(II)-carbenoid insertion step, which prefers insertion into hydroxyl groups with an adjacent axial substituent. The subsequent intramol. enolate protonation determines the unexpected high stereoselectivity. The most prevalent trans-1,2-diols in various pyranoses can be systematically and predictably differentiated based on the model derived from DFT calculations We also demonstrated that the selective O-alkylation method could significantly improve the efficiency and stereoselectivity of glycosylation reactions. The alkyl groups introduced to carbohydrates by OH insertion reaction can serve as functional groups, protecting groups, and directing groups.
Journal of the American Chemical Society published new progress about Alkylation. 4064-06-6 belongs to class alcohols-buliding-blocks, and the molecular formula is C12H20O6, Application In Synthesis of 4064-06-6.
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