Access to chiral bisphenol (bpol) ligands through desymmetrizing asymmetric ortho-selective mono-halogenation

Patent metadata

Field	Value
Publication number	US-2024166586-A1
Application number	US-202418416993-A
Country	US
Kind code	A1
Filing date	Jan 19, 2024
Priority date	Mar 30, 2020
Publication date	May 23, 2024
Grant date	—

Abstract

The subject invention pertains to a method of halogenating phenols, yielding a range of halogenated phenols with enantiomeric ratio of up to 99.5:0.5. In certain embodiments, the subject invention pertains to a method of asymmetric halogenation of bisphenol, yielding a range of chiral bisphenol ligands. The novel chiral bisphenols are potent privileged catalyst cores that can be applied to the preparation of ligands for various catalytic asymmetric reactions. The catalyst library can easily be accessed because late-stage modification of the scaffold can readily be executed through cross-coupling of the halogen handles on the bisphenols.

First claim

We claim:

1 . A chiral bisphenol, diesterphosphoric acid or phosphoroamidite therefrom, comprising an asymmetric ortho-halogenated bisphenol, an ortho-aromatic substituted bisphenol, a diesterphosphoric acid or a phosphoroamidite therefrom where the bisphenol is of the structure:

wherein:
a) X and X′ are respectively: Br and H; Cl and H; Br and Cl; 1-naphthyl and 2-napthyl; 3,5-ditrifluoromethylphenyl and 1-naphthyl; or 4-nitrophenyl and 1-naphthyl, and
b) R is: H; 4-Ph; 4-n-butyl; 4-t-butyl; 4-benzyl; 4-CMe 2 Ph; 4-phenoxy; 4-F; 4-Cl; 4,5-dimethyl; 4-methyl, 5-F; 4-methyl, 5-Cl; 4-F, 5-methyl; 4-(2-methoxyethyl); and 4-(2-acetoxyethyl) and wherein the enantiomeric ratio is at least 51:49.

2 . The chiral bisphenol diesterphosphoric acid or phosphoroamidite therefrom according to claim 1 , wherein the enantiomeric ratio is at least 59.5:40.5.

3 . The chiral bisphenol diesterphosphoric acid or phosphoroamidite therefrom according to claim 1 , wherein the enantiomeric ratio is at least 83.5:16.5.

4 . The chiral bisphenol diesterphosphoric acid or phosphoroamidite therefrom according to claim 1 , wherein the enantiomeric ratio is at least 94:6.

5 . The chiral bisphenol diesterphosphoric acid or phosphoroamidite therefrom according to claim 1 , wherein the enantiomeric ratio is at least 97.5:2.5.

6 . The chiral bisphenol diesterphosphoric acid or phosphoroamidite therefrom according to claim 1 , wherein the phosphoroamidite is a (+)-bis[(R)-1-phenylethyl]phosphoroamidite.

Assignees

• Univ Hong Kong Chinese

Inventors

• Yeung Ying-Yeung
• Xiong Xiaodong
• Zheng Tianyu
• Wang Xinyan
• Tse Ying-Lung Steve

Classifications

• C07C37/62 Primary

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• C07C37/18

  by condensation involving halogen atoms of halogenated compounds · CPC title

• C07C39/367

  polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes · CPC title

• C07F9/2404

  the ester moiety containing a substituent or a structure which is considered as characteristic · CPC title