Compound of 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based bisoxazoline ligand, intermediate thereof, preparation method thereof and use thereof

Patent metadata

Field	Value
Publication number	US-11220495-B2
Application number	US-201716955062-A
Country	US
Kind code	B2
Filing date	Dec 29, 2017
Priority date	Dec 22, 2017
Publication date	Jan 11, 2022
Grant date	Jan 11, 2022

Abstract

Provided are a compound of 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based bisoxazoline ligand, an intermediate, a preparation method and uses thereof. The compound of bisoxazoline ligand is a compound having a structure represented by formula I, or an enantiomer, a raceme, or diastereomer thereof. The bisoxazoline ligand can be prepared via a preparation scheme in which the cheap and easily available 6,6′-dihydroxyl-3,3,3′,3′-tetramethyl-1,1′-spirobiindane is used as a starting raw material and the compound represented by formula II serves as the key intermediate through a series of reactions. The new bisoxazoline ligand developed by the present application can be used in catalytic organic reaction, in particular as a chiral bisoxazoline ligand that is widely used in many asymmetric catalytic reactions of metal catalysis, and thus it has economic practicability and industrial application prospect.

First claim

What is claimed is:

1. A 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based bisoxazoline ligand, being a compound represented by formula I, or being an enantiomer, or a diastereomer thereof:

wherein R 1 and R 6 are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, and aryl; R 2 , R 3 , R 4 , and R 5 are each independently selected from hydrogen, or C 1 -C 10 alkyl; and R 7 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl, C 6 -C 14 aryl, and arylmethylene; R 8 and R 9 are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl, and C 6 -C 14 aryl.

2. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based bisoxazoline ligand according to claim 1 , wherein the compound represented by formula I is any one of the following compounds:

3. A method for preparing the compound of formula I according to claim 1 , comprising the following steps of:
using the compound of formula II as a starting material, preparing the compound of formula III through a potassium permanganate oxidation reaction, then carrying out an acyl chlorination reaction, condensing with aminoethanol compounds to form amide alcohol, and finally cyclizing to obtain the compound of formula I:

wherein, R 1 -R 9 are the same as those defined in claim 1 .

Assignees

• Univ Zhejiang

Inventors

• Lin Xufeng
• Gu Haorui
• Sun Weiye

Classifications

• C07D263/12 Primary

  with radicals containing only hydrogen and carbon atoms · CPC title

• C07B2200/13

  Crystalline forms, e.g. polymorphs · CPC title

• B01J2231/42

  Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement · CPC title

• C07D413/10 Primary

  linked by a carbon chain containing aromatic rings · CPC title

• B01J2531/842

  Iron · CPC title