TMSOTf-Catalyzed Silylation: Streamlined Regioselective One-Pot Protection and Acetylation of Carbohydrates

• Published in: European Journal of Organic Chemistry Vol. 2012; no. 4; pp. 744 - 753
• Main Authors: Joseph, A. Abragam, Verma, Ved Prakash, Liu, Xin-Yi, Wu, Chia-Hui, Dhurandhare, Vijay M., Wang, Cheng-Chung
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.02.2012; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Carbohydrates; Carbohydrates with 4, 5, 6, ... C atoms, dissacharides and oligosaccharides; Carbohydrates. Nucleosides and nucleotides; Chemistry; Chemistry, Organic; Exact sciences and technology; Glycosides; Organic chemistry; Physical Sciences; Preparations and properties; Protecting groups; Science & Technology; Synthetic methods; Carbohydrates; ALPHA-TRIMETHYLSILYLOXYPHOSPHONATES; ACYLATION REACTION; HEXAMETHYLDISILAZANE HMDS; CARBONYL-COMPOUNDS; ACID ANHYDRIDES; HIGHLY EFFICIENT METHOD; TRIMETHYLSILYL ETHERS; ALCOHOLS; MILD; PHENOLS; Protecting groups; Glycosides; Synthetic methods; One pot reaction; Protecting group; Catalytic reaction; Regioselectivity; Trehalose; Silylation; Oside; Monosaccharides; Glycoside; Acetylation; Chemical synthesis; Protection; Trifluoromethanesulfonic acid trimethylsilyl ester
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201101267

A highly efficient TMSOTf‐catalyzed HMDS silylation of sugars, which can easily be integrated with subsequent reactions in one‐pot fashion, has been developed. Its usefulness was demonstrated by applications to streamlined regioselective one‐pot protection and nonenzymatic acetylation of unprotected sugars. Monosaccharide and trehalose building blocks with orthogonally well‐differentiated hydroxy groups were efficiently prepared starting with free sugars in one‐pot fashion without the need for prior per‐O‐silylation. Regioselectively protected and acetylated building blocks were prepared directly from unprotected sugars in a one‐pot manner involving up to five TMSOTf‐catalyzed reactions, including a new TMSOTf‐catalyzed silylation of carbohydrates.