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Synthesis and applications of oxaspiro PNN ligand

A technology of oxaspiro and ligands, which is applied in the field of synthesis of novel oxaspirocyclic bisphosphine ligands, can solve the problems of limited substrate range and loss of activity of the catalytic system, and achieve high enantioselectivity

Active Publication Date: 2019-08-16
SHENZHEN CATALYS SCI & TECH CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are still many defects in its catalytic system. For example, some functionalized ketones can replace the diamine ligand Anaiji to deactivate the catalytic system, resulting in a limited range of substrates; another example is chiral bisphosphine ligands and chiral Stereoeffects of sexual diamine ligands must be precisely matched to achieve high enantioselective results

Method used

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  • Synthesis and applications of oxaspiro PNN ligand
  • Synthesis and applications of oxaspiro PNN ligand
  • Synthesis and applications of oxaspiro PNN ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] (S)-4'-(Di-3,5-di-tert-butylphenylphosphinooxy)-2H,2'H-3,3'-spirobis[benzofuran]-4-trifluoromethane Synthesis of sulfonate 2a:

[0030]

[0031] N 2 Under atmosphere, add 1 (5.2g, 10mmol), dppb (213mg, 0.05mmol), Ar 2 POH (6.39g, 15mmol), Pd(PAc) 2 (112mg, 0.05mmol) and DIPEA (6.5mL, 40mmol), and finally 50mL of anhydrous and oxygen-free DMSO was added. Reaction at 100°C for 6h. After being cooled to room temperature, water was added to quench the reaction, and the reaction system was extracted with ethyl acetate. The organic phase was dried with anhydrous sodium sulfate and the solvent was removed under reduced pressure. After simple column chromatography, the product 2a (7.43 g, yield = 93%).

[0032] white solid. 1 H NMR (500MHz, CDCl 3 )δ1.18(s,9H,CH 3 ),1.19(s,9H,CH 3 ),1.20(s,9H,CH 3 ),1.21(s,9H,CH 3 ),4.54-4.56(m,1H,CH 2 ),4.62-4.64(m,1H,CH 2 ),4.80-4.82(m,2H,CH 2 ),6.63-6.68(m,2H,Ar),6.82-6.88(m,6H,Ar),6.90-6.94(m,2H,Ar),7.15-7.21(m,1H,Ar),7.26-...

Embodiment 2

[0034] (S)-4'-(Di-3,5-di-tert-butylphenylphosphino)-2H,2'H-3,3'-spirobis[benzofuran]-4-trifluoromethanesulfonic acid Synthesis of ester 3a:

[0035]

[0036]In a sealed 100 mL tube, 2a (3.98 g, 5 mmol), DIPEA (6.6 mL, 40 mmol), 20 mL of toluene and trichlorosilane (2.0 mL, 20 mmol) were added. The reaction was stirred overnight at 120°C. The reaction system was quenched with excess saturated sodium bicarbonate solution, 100 mL of ethyl acetate was added, filtered through diatomaceous earth, and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, followed by column chromatography to obtain white solid 3a (3.51 g, yield = 90%).

[0037] white solid. 1 H NMR (500MHz, CDCl 3 )δ1.17(s,9H,CH 3 ),1.19(s,9H,CH 3 ),1.20(s,9H,CH 3 ),1.21(s,9H,CH 3 ),4.52-4.55(m,1H,CH 2 ),4.60-4.63(m,1H,CH 2 ),4.77-4.82(m,2H,CH 2 ),6.61-6.69(m,2H,Ar),6.80-6.94(m,6H,Ar),7.14-7.22(m,2H,Ar),7.28-7.34(m,2H,Ar). 13 C{1H}NMR (126MHz, CDCl 3...

Embodiment 3

[0039] Preparation of (S)-4-bis-3,5-di-tert-butylphenylphosphoryl-2H,2'H-3,3'-spirodibenzotetrahydrofuran-4-carboxylic acid 4a:

[0040]

[0041] Into a 250 mL reactor was charged palladium acetate (259 mg, 1.16 mmol) and 1,3-bis(diphenylphosphine)propane (478 mg, 1.16 mmol), 3a (5.51 g, 7.0 mmol). The autoclave was then transferred to a glove box, and dimethyl sulfoxide (60 mL) was added followed by methanol (42 mL) and triethylamine (11.6 mL). The reaction kettle was then removed from the glove box, and the pressure of carbon monoxide was increased to 10 atm. Then the reaction kettle was placed on a 70°C oil bath and stirred overnight. After the reaction was completed, the reaction mixture was transferred to a 500mL separatory funnel and 250mL of ethyl acetate was added, then the organic phase was washed twice with saturated brine, the organic phase was dried, and the solvent was removed by column chromatography to obtain the methyl ester product, which was then subjecte...

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Abstract

The invention belongs to the field of chiral synthesis, and specifically provides synthesis of a class of novel oxaspiro PNN ligands. According to the synthesis, oxaspiro diphenol is used as a starting raw material, and trifluoromethyl sulfonylation, palladium-catalyzed diarylphosphine oxide coupling, trichlorosilane reduction, palladium-catalyzed carbon insertion esterification, hydrolysis, amination, reductive amination and other steps are performed to synthesize the novel oxaspiro PNN ligand. According to the present invention, the oxaspiro compound has central chirality, such that the novel oxaspiro PNN ligands comprise the levo-oxaspiro PNN ligand and the dextro-oxaspiro PNN ligand, and the racemic oxaspiro PNN ligand can be synthesized by using the racemic oxaspiro diphenol as the raw material; and the PNN ligand can be used as the chiral ligand for the asymmetric hydrogenation of ketone and lactone, wherein the complex of the ligand and iridium can respectively obtain the enantioselectivity of more than 98% and more than 99% in the asymmetric hydrogenation of simple ketones and lactones.

Description

technical field [0001] The invention relates to the synthesis of a novel oxaspirocyclic bisphosphine ligand. The compound can be used as a chiral ligand in asymmetric catalytic reactions, has high potential application value in the field of asymmetric catalysis, and belongs to the field of asymmetric catalysis. Background technique [0002] In 1987, Noyori initiated a revolution in the asymmetric hydrogenation of functionalized ketones with BINAP / Ru(OCOCH3)2 / HCl. Later, his chiral bisphosphine / ruthenium / bisamine catalyst expanded the range of substrates to non-functional Ketones ((a) Noyori R. et al. J. Am. Chem. Soc. 1987, 109, 5856; (b) Ohkuma T. et al. J. Am. Chem. Soc. 1995, 117, 2675). However, there are still many defects in its catalytic system. For example, some functionalized ketones can replace the diamine ligand Anaiji to deactivate the catalytic system, resulting in a limited range of substrates; another example is chiral bisphosphine ligands and chiral The ste...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6561B01J31/24C07B53/00C07B31/00C07C29/145
CPCB01J31/249B01J2231/641B01J2231/643B01J2531/0241B01J2531/822C07B31/00C07B53/00C07B2200/07C07C29/145C07F9/6561
Inventor 张绪穆陈根强黄佳明
Owner SHENZHEN CATALYS SCI & TECH CO LTD
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