3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based phosphinooxazoline ligand compound, preparation method and uses of the same

Patent metadata

Field	Value
Publication number	US-11111258-B2
Application number	US-201816959672-A
Country	US
Kind code	B2
Filing date	Jan 8, 2018
Priority date	Jan 3, 2018
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

The invention discloses a tetramethyl-7,7′-spirobiindane-based phosphinooxazoline ligand compound and its preparation method and use. The phosphinooxazoline ligand compound is a compound having a structure shown in general formula I or an enantiomer, a raceme or a diastereoisomer thereof. The phosphinooxazoline ligand obtained through a series of reaction steps using cheap and easily available 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-6,6′-diol as a starting material. The novel phosphinooxazoline ligand developed in the invention can be used to organic catalytic reactions, especially as a chiral phosphinooxazoline ligand widely used in metal-asymmetric catalytic reactions, having economical practicality and industrial application prospects.

First claim

What is claimed is:

1. A 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based phosphinooxazoline ligand, being a enantiomer or a diastereoisomer of a compound represented by formula I:

wherein R 1 and R 6 are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6 cycloalkyl, and C 1 -C 4 alkoxy or perfluoroalkoxy; R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 10 alkyl or perfluoroalkyl, and C 3 -C 6 cycloalkyl; R 7 is selected from the group consisting of hydrogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6 cycloalkyl, C 6 -C 14 aryl, CMe 2 OBn, CMe 2 Ph, CMePh 2 , CPh 3 , CH(Ph)OMe, and CH(Ph)OBn; R 8 and R 9 are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6 cycloalkyl, C 6 -C 14 aryl, CH 2 OCHPh 2 , CH 2 OCPh 3 , and CH 2 OCH 2 Ph; and R 10 is selected from the group consisting of C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6 cycloalkyl, and C 6 -C 14 aryl.

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

3. A preparation method of the compound I according to claim 1 , comprising the following steps:
preparing a compound represented by formula III through a mono-substitution reaction of a compound represented by formula II, as a starting material, with disubstituted phosphine halide under an effect of an alkali, subjecting the compound represented by formula III to a palladium-catalyzed cyanation, an acidic hydrolysis, and a condensation reaction with an aminoethanol compound to form amphenicol, and then conducting a cyclization reaction to obtain the compound represented by formula I, as the following reaction scheme:

wherein R 1 -R 10 in the formula I are the same as those defined in claim 1 ; X in the formula II is bromine or iodine; and
wherein EDCI is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and HOBt is 1-hydroxylbenzotriazole.

Assignees

• Univ Zhejiang

Inventors

• Lin Xufeng
• Sun Weiye
• Gu Haorui

Classifications

• B01J2531/16

  Copper · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J2231/4205

  C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type · CPC title

• B01J2531/0241

  Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution · CPC title

• C07D291/08

  condensed with carbocyclic rings or ring systems · CPC title