A General Method for the Synthesis of Cyclodextrinyl Aldehydes and Carboxylic Acids

Abstract

The selective synthesis of the primary-side monoaldehyde of /3-cyclodextrin, 6-deoxy-6-formyl-/3cyclodextrin, was accomplished by oxidation of the corresponding tosylate utilizing the Nace reaction (DMSO/collidine). This monoaldehyde was then used as the starting material in several reactions including reduction, addition of NaHS03, addition of the a-nucleophiles hydroxylamine and hydrazine, and reductive amination. Of particular interest is the conversion of the monoaldehyde to the primary side carboxylic acid, 6-deoxy-6-carboxy-/3-cyclodextrin, via bromine oxidation. This general method sequence can be applied to any tosyl derivative of cyclodextrin as demonstrated in the synthesis of /3-cyclodextrin-A,D-dialdehyde and /3-cyclodextrin-A,D-diacid.

Resveratrol Functionalized Carboxymethyl-β-Cyclodextrin: Synthesis, Characterization, and Photostability

“…In comparison, the 1 H NMR spectra of CM-β-CD did not include the peaks of aromatic ring. In the 13 C NMR spectrum of CDRes, the signal at 172.14 ppm was assigned to carbon atom of the carboxyl groups of the CM-β-CD [32]. e signal at 163.49 was assigned to the ester bond [33].…”

Artificial Glycosyl Phosphorylases

“…Synthesis of 1, 2 and 14: Compounds 1 and 2 [18][19][20] were readily obtained from the diols 8 and 9, made in turn by selective O-debenzylation of 6 or 7 by Pearce and Sinaþs procedure (Scheme 1). [21,22] This powerful method uses diisobutylaluminum hydride (DIBAL) in toluene to remove one ormore importantly-two benzyl groups from the perbenzylated CD in a selective fashion.…”

“…A ,6 D -dicarboxylic acid (2): [18][19][20] Compound 9 (2.2 g, 0.76 mmol) was dissolved in an AcOEt/MeOH mixture (1:1, 150 mL). Pd/C (300 mg) and TFA (cat.)…”

“…After the system had been stirred for 3 h at 40 8C the solvent was removed in vacuo. The remaining oil was purified by column chromatography on silica gel (eluent, CH 2 (19): An aqueous solution of sodium hydroxide (4 m, 5 mL) was added to a solution of 18 (600 mg, 0.24 mmol) in MeOH (10 mL). After stirring overnight at room temperature, the reaction mixture was diluted with water (10 mL) and Amberlite IR-120 (H + form) until pH neutral, and the mixture was filtered and concentrated in vacuo.…”

Synthesis of Novel β-Cyclodextrin and Calixarene Derivatives and Their Use in Gas Sensing on the Basis of Molecular Recognition

“…[42] Mono(6-benzylimino-6-deoxy)-β-cyclodextrin (4): 6-OTs-β-CD was converted into 6-β-cyclodextrin monoaldehyde by oxidizing with DMSO at 80°C. [43] Benzylamine (30 mL) and monoaldehydic β-cyclodextrin (1 g) were dissolved in 30 mL mixed solvent of water and methanol (v/v: 1:2), and several drops of acetic acid were added to catalyze the reaction. The reaction mixture was stirred at room temperature under N 2 for five days, and the solvent was then evaporated under reduced pressure.…”