Abstract: Confinement is a unifying element in selective enzymic reactions but has rarely been used to control site selectivity of carbon-hydrogen (C-H) bond functionalization in artificial receptors. Herein, we demonstrate the selective functionalization of one of seven C(sp3)-H bonds on a D-glucopyranosyl residue of γ-cyclodextrin (γ-CD) by irradiating 2-benzoylbenzoate in a γ-cyclodextrin-containing metal-organic framework (CD-MOF-1). Both 1H NMR spectroscopy and X-ray crystallog. of the products confirm that functionalization occurs selectively at one of the two C(sp3)-H bonds on the C6 position of a D-glucopyranosyl residue. The alignment of 2-benzoylbenzoate inside (γ-CD)2 tunnels in CD-MOF-1, as revealed by X-ray crystallog., precludes C-H functionalization on the outer surface of the γ-CD tori. Theoretical calculations indicate less steric hindrance associated with C6-functionalized (γ-CD)2 tunnels in CD-MOF-1 compared with C3 and C5, leading to the observed site selectivity.
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With 2,6-di-tert-butyl-4-methyl-phenol; tetrabutylammomium bromide; In ISOPROPYLAMIDE; acetonitrile; for 16.0h;Reflux;
Synthesis of BP-3; [0145] Synthesis of 2-benzoyl-benzoic acid 3-(4-acryloyloxy-butoxy)-2-hydroxy- propyl ester:A reaction mixture containing 2-benzoyl benzoic acid (40.0 g), acetonitrile(300 mL), dimethylacetamide (10 ml_), tetrabutylammonium bromide (5.6 g)and 2,6-di-tert-butyl-4-methylphenol (0.3 g) was heated to reflux.At this temperature 4-hydroxybutylacrylate glycidylether (28.0 g) was added and the mixture was allowed to stir at reflux temperature for 16 hours.The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure.The residual oil was dissolved in methyl-tert-butylether (300 mL) and extracted 3 times with a mixture of an aqueous solution of sodium hydroxide (1 N) and distilled water (1/2.4)The organic layer was separated, dried on MgSO4, filtered and evaporated to provide 45.2 g of a brown oil.
With 2,6-di-tert-butyl-4-methyl-phenol;tetrabutylammomium bromide; In N,N-dimethyl acetamide; acetonitrile; for 16.0h;Reflux;
A reaction mixture containing 2-benzoyl benzoic acid (40.0 g), acetonitrile (300 mL), dimethylacetamide (10 mL), tetrabutylammonium bromide (5.6 g)and 2,6-di-tert-butyl-4-methylphenol (0.3 g) was heated to reflux. At this temperature 4-hydroxybutylacrylate glycidylether (28.0 g) was added and the mixture was allowed to stir at reflux temperature for 16 hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The residual oil was dissolved in methyl-tert-butylether (300 mL) and extracted 3 times with a mixture of an aqueous solution of sodium hydroxide (1N) and distilled water (1/2.4). The organic layer was separated, dried on MugsO4, filtered and evaporated to provide 45.2 g of a brown oil.
45.2 g
With 2,6-di-tert-butyl-4-methyl-phenol; tetrabutylammomium bromide; In N,N-dimethyl acetamide; acetonitrile; for 16.0h;Reflux;
Synthesis of 2-benzoyl-benzoic acid 3-(4-acryloyloxy-butoxy)-2-hydroxy-propyl ester A reaction mixture containing 2-benzoyl benzoic acid (40.0 g, 0.1722 mol), acetonitrile (300 mL), dimethylacetamide (10 mL), tetrabutylammonium bromide (5.6 g, 17.22 mmol) and 2,6-di-tert-butyl-4-methylphenol (0.3 g, 1.4 mmol) was heated to reflux. At this temperature 4-hydroxybutylacrylate glycidylether (28.0 g, 140 mmol) was added and the mixture was allowed to stir at reflux temperature for 16 hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The residual oil was dissolved in methyl-tert-butylether (300 mL) and extracted 3 times with a mixture of an aqueous solution of sodium hydroxide (1N) and distilled water (1/2.4) The organic layer was separated, dried on MgSO4, filtered and evaporated to provide 45.2 g of a brown oil.
With sodium hydroxide; tetrabutylammomium bromide; In tert-butyl methyl ether; ISOPROPYLAMIDE; water; acetonitrile;
Synthesis of BP-3 Synthesis of 2-benzoyl-benzoic acid 3-(4-acryloyloxy-butoxy)-2-hydroxy-propyl ester: A reaction mixture containing 2-benzoyl benzoic acid (40.0 g, 0.1722 mol), acetonitrile (300 mL), dimethylacetamide (10 mL), tetrabutylammonium bromide (5.6 g, 17.22 mmol) and 2,6-di-tert-butyl-4-methylphenol (0.3 g, 1.4 mmol) was heated to reflux. At this temperature 4-hydroxybutylacrylate glycidylether (28.0 g, 140 mmol) was added and the mixture was allowed to stir at reflux temperature for 16 hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure. The residual oil was dissolved in methyl-tert-butylether (300 mL) and extracted 3 times with a mixture of an aqueous solution of sodium hydroxide (1N) and distilled water (1/2.4) The organic layer was separated, dried on MgSO4, filtered and evaporated to provide 45.2 g of a brown oil.
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