Axially chiral biaryl compound with P-stereo center and synthesis method and application thereof

A synthesis method and compound technology, which can be used in organic chemistry methods, preparation of organic compounds, organic compounds/hydrides/coordination complex catalysts, etc. The effect of enantioselectivity, mild reaction conditions, and simple operation

Inactive Publication Date: 2021-08-24
SHAANXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Such extraordinary selectivity has only been reported in two cases, but no enantioselective catalytic system has yet been developed

Method used

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  • Axially chiral biaryl compound with P-stereo center and synthesis method and application thereof
  • Axially chiral biaryl compound with P-stereo center and synthesis method and application thereof
  • Axially chiral biaryl compound with P-stereo center and synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Synthesis of (S)-N,N-diisopropyl-P-phenyl-P-((R))-2-(2,3,4-triphenyl-1-naphthyl)phenyl with the following structural formula ) Phosphinamide

[0027]

[0028] Under nitrogen atmosphere, add 30.1mg (0.1mmol) N,N-diisopropyl-P,P-diphenylphosphinamide, 44.6mg (0.25mmol) toluene, 4.6mg ( 0.004mmol) [Cp X Rh(III)], 4.1mg (0.016mmol) silver trifluoromethanesulfonate, 41.8mg (0.25mmol) silver acetate, 25.6mg (0.2mmol) cyclohexyl formic acid, 2mL dichloromethane, tighten the pressure tube, 60℃ The reaction was stirred for 24 hours. After the reaction was completed, the dichloromethane was removed by rotary evaporation under reduced pressure to obtain a crude product. The crude product was passed through a column with silica gel (petroleum ether:ethyl acetate=10:1~5:1) to obtain a light yellow solid product , and its yield is 71% (yield is calculated based on phosphoramide), and the characterization data are: 1 H NMR (600MHz, CDCl 3 )δ8.05–7.97(m,1H),7.63–7.54(m,3H),7.46–...

Embodiment 2

[0030] Synthesis of (S)-N,N-diisopropyl-P-((R))-4-methoxy-2-(2,3,4-triphenyl-1-naphthyl)benzene with the following structural formula base)-P-(4-methoxyphenyl)phosphinamide

[0031]

[0032] In this example, the N,N-diisopropyl group used in Example 1 was replaced with equimolar N,N-diisopropyl-P,P-bis(4-methoxyphenyl)phosphinamide -P, P-diphenylphosphinamide, other steps are the same as in Example 1, to obtain a light yellow solid product, the yield is 60%, and the characterization data are: 1 H NMR (600MHz, CDCl 3 )δ7.92(dd,J=11.5,8.9Hz,1H),7.52–7.43(m,4H),7.35–7.27(m,3H),7.24–7.17(m,2H),7.16–7.14(m, 2H),6.92(d,J=8.7Hz,1H),6.88–6.74(m,6H),6.74–6.64(m,5H),6.47(d,J=7.5Hz,1H),6.28(t,J =7.5Hz,1H),3.78(s,3H),3.69(s,3H),3.44–3.51(m,2H),1.13(d,J=6.7Hz,6H),1.05(d,J=6.7Hz ,6H); 13 C NMR (151MHz, CDCl 3 )δ161.1(d, J=2.8Hz), 160.4(d, J=2.7Hz), 146.1(d, J=11.4Hz), 140.9, 140.3, 139.7, 138.5, 138.2, 138.0, 138.0, 137.1, 135.0 (d,J=9.5Hz),134.2(d,J=10.9Hz),132.9,131.7,131.7,131....

Embodiment 3

[0034] Synthesis of (S)-P-((R)-4-fluoro-2-(2,3,4-triphenyl-1-naphthyl)phenyl)-P-(4-fluorophenyl) with the following structural formula -N,N-Diisopropylphosphinamide

[0035]

[0036] In this example, N,N-diisopropyl-P,P-bis(4-fluorophenyl)phosphinamide used in Example 1 was replaced with equimolar N,N-diisopropyl-P , P-diphenylphosphinamide, equimolar silver hexafluoroantimonate instead of silver trifluoromethanesulfonate used in Example 1, other steps are the same as Example 1, to obtain light yellow solid product, its yield is 80%, the characterization data is: 1 H NMR (600MHz, CDCl 3 )δ8.02–7.98(m,1H),7.55(d,J=8.0Hz,1H),7.53–7.48(m,2H),7.40–7.37(m,2H),7.36–7.34(m,2H) ,7.32–7.29(m,1H),7.21–7.17(m,2H),7.18–7.13(m,1H),7.10–7.04(m,2H),6.94–6.83(m,6H),6.83–6.77( m,2H),6.73(t,J=7.3Hz,1H),6.70–6.66(m,1H),6.49(d,J=7.6Hz,1H),6.35(t,J=7.4Hz,1H), 3.46–3.39(m,2H),1.14(d,J=6.7Hz,6H),1.07(d,J=6.8Hz,6H); 13 C NMR (151MHz, CDCl 3 )δ164.1 (dd, J=3.3, 251.8Hz), 163.3 (dd, J=3.2, 25...

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Abstract

The invention discloses an axially chiral biaryl compound with a P-stereo center and a synthesis method and application thereof. The structural formula of the compound is shown in the specification, chiral trivalent rhodium [CpXRh(III)] is used as a catalyst, diaryl phosphonamide and diaryl acetylene are used as raw materials, and enantioselective coupling is conducted under the assistance of silver trifluoromethanesulfonate or silver hexafluoroantimonate and silver acetate to obtain the compound. Diarylacetylene is taken as an initial raw material, the compound is stable in property and easy to prepare, but the compound is seldom applied to arylation reaction. In the prior art, aryl arylation is mainly carried out by using brominated aromatic hydrocarbon, arylboronic acid and the like. The simple diarylacetylene is adopted as an arylation reagent, the axially chiral biaryl and the P-center chiral compound are stereoscopically and specifically synthesized through double activation of C-H bonds in the aryl phosphonamide and the diarylacetylene, and the method has the advantages of being mild in reaction condition, high in enantioselectivity, good in diastereoselectivity and the like.

Description

technical field [0001] The invention relates to an axial chiral biaryl compound with a P-stereocenter, a method for catalytically synthesizing the compound with trivalent rhodium and its application. Background technique [0002] Atropisomeric chiral compounds are a class of compounds widely used in aromatic compounds. They have important applications in pharmaceutical reagents, organic molecular catalysts, and chiral ligands. They have received extensive attention and research, and have been developed Many methods have been proposed to synthesize biaryl compounds, mainly including organomolecular catalysis and metal catalysis. Although some progress has been made, there are still some challenges to be improved, such as the need to use stoichiometric chiral auxiliaries and the need to prefunctionalize starting materials, so overcoming the above limitations has become a general trend in the synthesis of such targeted compounds . In this regard, asymmetric C-H bond activatio...

Claims

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Application Information

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IPC IPC(8): C07F9/36C07F9/50B01J31/22B01J31/24C07C67/343C07C69/618
CPCC07F9/36C07F9/5022C07F9/509B01J31/2409B01J31/187C07C67/343B01J2531/824B01J2231/4205C07B2200/07C07C69/618
Inventor 李兴伟王芬胡盼洁
Owner SHAANXI NORMAL UNIV
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