Compound of 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based phosphine ligand, and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11530230-B2
Application number	US-201716770956-A
Country	US
Kind code	B2
Filing date	Dec 14, 2017
Priority date	Dec 13, 2017
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

The present application discloses a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based phosphine ligand, an intermediate, a preparation method and uses thereof. The compound of phosphine ligand is a compound having a structure represented by formula I or formula II, or an enantiomer, a raceme, or diastereomer thereof. The phosphine 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 raw material and the compound represented by formula III serves as the key intermediate. The new phosphine ligand developed by the present application can be used in catalytic organic reaction, in particular as a chiral phosphine ligand that is widely used in many asymmetric catalytic reactions including asymmetric hydrogenation and asymmetric allyl alkylation, 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 phosphine ligand, being a compound represented by formula I or formula II, or being an enantiomer, a raceme 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 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, C 3 -C 6 cycloalkyl, and C 1 -C 4 alkoxy or perfluoroalkoxy; and R 7 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. A synthesis method of the compound represented by formula I according to claim 1 , wherein a racemic or optically active compound represented by formula III, as a raw material, reacts with a di-substituted phosphine halide under an effect of an alkali to obtain the compound represented by formula I via a double-substitution reaction in accordance with the following reaction equation:

or
wherein the compound represented by formula III and a di-substituted phosphine oxyhalide are subjected to a double-substitution reaction under an effect of an alkali to prepare a compound represented by formula 6, which is then subjected to a reduction reaction to prepare the compound represented by formula I, in accordance with the following reaction equation:

and
wherein X is halogen, and R 1 -R 7 are the same as those defined in claim 1 .

3. A synthesis method of the compound represented by formula II according to claim 1 , wherein a racemic or optically active compound represented by formula III, as a raw material, reacts with di-substituted phosphine halide under an effect of an under alkali to obtain the compound represented by the formula II via a mono-substitution reaction in accordance with the following reaction equation:

or
wherein the compound represented by formula III and di-substituted phosphine oxyhalide are subjected to a mono-substitution reaction under an effect of an alkali to prepare a compound represented by formula 7, which is then subjected to a reduction reaction to prepare the compound represented by formula II, in accordance with the following reaction equation:

and
wherein X is halogen, and R 1 -R 7 are the same as those defined in claim 1 .

Assignees

• Univ Zhejiang

Inventors

• Lin Xufeng
• Yao Linxi
• Chang Shirui
• Wang Lei

Classifications

• C07F9/5022 Primary

  Aromatic phosphines (P-C aromatic linkage) · CPC title

• B01J31/249

  Spiro-condensed ring systems · CPC title

• B01J31/2457

  comprising aliphatic or saturated rings, e.g. Xantphos · CPC title

• C07F9/5027 Primary

  Polyphosphines · CPC title

• C07C17/06

  combined with replacement of hydrogen atoms by halogens · CPC title