Economical and practical resolution method of 2, 2 '-diphenol compound

Abstract

The invention discloses a resolution method of a 2, 2 '-diphenol compound. The method comprises the following steps: dissolving despinner 6, 6 '-dimethyl-3, 3'-di-tert-butyl-5, 5 '-dibromo-2, 2'-diphenol and sodium hydride into tetrahydrofuran, reacting with (R)-2-methoxyphenylacetyl chloride at room temperature, and separating and purifying to obtain a mono-esterification product with the yield of 49% and the diastereoisomer selectivity of more than 99%, and a di-esterification product with the yield of 32% and the diastereoisomer selectivity of more than 99%; dissolving the obtained single esterification product or double esterification product and lithium aluminum hydride in tetrahydrofuran respectively, reacting at 0 DEG C to room temperature, and purifying to obtain the 2, 2 '-diphenol compound with the yield of 96% and the enantiomer selectivity of more than 99%. The resolution method iseasy to operate, mild in condition and high in yield.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and more specifically relates to an economical and practical method for resolving 2,2'-biphenol compounds. Background technique [0002] Biphenyls are a class of compounds that do not contain chiral centers but have C 2 Atropisomeric compounds with axes of symmetry. Its chemical properties are highly similar to binaphthyl compounds: axial symmetry, rigidity, high stability of chiral configuration and high reaction site modification, etc. Taking advantage of its excellent chemical properties, Maruoka's group used the chiral biphenyl compound [(S)-6,6'-dimethyl-3,3'-di-tert-butyl-5,5'-dibromo-2, 2'-biphenol] was used as an important precursor to synthesize a series of biphenyl chiral quaternary ammonium salt phase transfer catalysts. These biphenyl chiral quaternary ammonium salt phase transfer catalysts are used in the reaction of N-diphenylmethylene glycine tert-butyl ester with di...

AI Technical Summary

Problems solved by technology

Maruoka's group early chiral resolution of biphenyl derivatives (6,6'-dimethyl-3,3'-di-tert-butyl-5,5'-dibromo-2,2'-biphenol) , with (R,R)-diphenylethylenediamine as the resolving agent, the chemical resolution was carried out through the salt-forming reaction with the axial chiral biphenol racemate, and the single biphenyl derivative after resolution The enantiomeric excess value (ee value) of the compound is >99%. However, (R,R)-diphenylethylenediamine is expensive as a resolving agent, which is not conducive to industrial production

Images