Design, Synthesis And Application Of Chiral Chemical Shift Reagents With Binol As A Core Scaffold

The determination of optical purity for chiral compounds has hugely potential application because of its advantages such as rapidity in measurement,simple operation and without separation of products.The results reported were rarely used for the reason of comlex molecular structure which was diffucult to be prepared or small chemical shift difference.In the study of carboxylic acid substrates,some chiral shift reagents have excellent nuclear chemical shift discrimination for carboxylic acids,but in the study of alcohols and amine substrates,no ideal results have obtained.The specific research content is as follows.First,pure compounds of(R,S)-Py-Binol-1a and(R,R)-Py-Binol-1b were designed and synthesized from Binol and proline.The synthetical reaction conditions were been optimized.Method to prepare optical pure chiral chemical shift reagents were been obtained.Second,application of(R,S)-Py-Binol-1a and(R,R)-Py-Binol-1b compound that was used as chiral solvating reagents to carboxylic acids was explored.NMR experiments have shown that excellent result was been obtained.The results show that the recognition of carboxylic acid is more extensive than previous chiral solvating reagents.It can show excellent recognition effect from aliphatic carboxylic acids to aromatic carboxylic acids.The best data of chemical shift defference was up to 386 Hz,and an excellent chiral chemical shift reagent was developed.Third,compoud of(R)-2,2'-dimethoxy-1,1'-binaphthyl-3-carboxylic acid chloride was prepared from R-Binol as a raw material.And its application to amine and alcohol was explored.It was found that it can not be successfully used as chiral chemical shift reagent.