Using DMF as Both a Catalyst and Cosolvent for the Regioselective Silylation of Polyols and Diols

Abstract

Highly regioselective silylation of primary hydroxyl groups of unprotected polyols and diols was obtained by the use of a mixed solvent of MeCN/DMF (10:1) in this study. DMF was discovered to be a good catalyst in this reaction, although the silylation using DMF as a solvent has been a common method for more than 40 years. The catalytic mechanism of DMF for the silylation was also proposed herein after intensive investigation of the reaction by NMR techniques. It has been demonstrated that a complex with a 1:1 ratio of the binding partners can be formed between TBSCl and DMF and has an association constant of 12/M, thus activating the silylation.

Selective modifications of unprotected carbohydrates for cross-linking in waterborne coatings

“…H-NMR (CDCl3): δ 4.71 (d, J = 3.6 Hz, 1H), 4.29 (s, 3H), 3.87 (dd, J = 10.8 & 3.2 Hz, 1H), 3.81-3.73 (m, 2H), 3.58-3.53 (m, 1H), 3.49 (dd, J = 9.6 & 3.6 Hz, 1H), 3.43-3.37 (m, 4H), 0.89 (s, 9H), 0.05 (s, 6H).Spectral data corresponded with literature 78. 6-O-trityl-α-methyl-ᴅ-glucopyranosideThis substrate was synthesized by I. C. Wan following the literature procedure of Gadakh et al 71 1 H-NMR (MeCN-d3): δ 7.52-7.46 (m, 6H), 7.37-7.31 (m, 6H), 7.30-7.24 (m, 3H), 5.11 (d, J = 4.3 Hz, 1H), 4.50-4.38 (m, 1H), 4.28 (d, J = 9.8, 5.1, 1.5 Hz, 1H), 3.77-3.72 (m, 1H), 3.62 (d, J = 5.3 Hz, 1H), 3.57(d, J = 7.9 Hz, 1H), 3.42 (s, 3H), 3.40-3.28 (m, 2H).Reactivity & selectivity of Fe(II) complexes with pyridyl-amine-based ligands for the oxidation of carbohydrates with H2O2…”

“…This substrate was synthesized according to the literature procedure of Dong et al 78 Spectral data corresponded with literature. 71 (4aR,6S,7R,8R,8aS)- Spectral data corresponded with literature.…”

Polysilicate Porous Organic Polymers (PSiPOPs), a Family of Porous, Ordered 3D Reticular Materials with Polysilicate Nodes and Organic Linkers

“…Following the successful synthesis of this pentanediol-linked PSiPOP, an isoreticular PSiPOP series was generated, implementing ethylene glycol and 1,7-heptanediol as alternative linkers. Instead of pyridine, , for these syntheses, , DMF was used to promote the reaction of octakis (dimethylsilyl chloride) spherosilicates with the alcohols. While this demonstrates that any catalyst with a proven track record in “Corey’s method” can probably be used for these syntheses, evaluating their relative performance falls outside the scope of the present work.…”

Glycoconjugates of Mucochloric Acid—Synthesis and Biological Activity

“…Next, 3,4,5-trichloro-furan-2(5H)-one reacted with propargylamine in 1,4-dioxane to obtain 8 in 45% yield [22]. Finally, N-propargyl-3,4-dichloro-5-hydroxy-2H-pyrrol-2-one 8 reacted with triisopropylsilyl chloride in the presence of imidazole and trimethylamine to obtain product 9 in 71% yield [42,43].…”

“…Cells survival fractions (SF) followed by 72 h MTT viability assay are presented in Supplementary File S1. chloro-5-hydroxy-2H-pyrrol-2-one 8 reacted with triisopropylsilyl chloride in the presence of imidazole and trimethylamine to obtain product 9 in 71% yield [42,43].…”