Method for defluorination alkylation and defluorination protonation reaction by using o-phosphinophenol photocatalyst

A photocatalyst and defluorinated alkyl technology, applied in catalytic reaction, organic chemical method, cyanide reaction preparation, etc., can solve the problems of high cost, environmental pollution, etc., and achieve the effects of prolonging life, simplifying treatment methods, and mild conditions

Pending Publication Date: 2021-12-28
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The photocatalysts widely used in these transformations are noble metal-based polypyridine complexes

Method used

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  • Method for defluorination alkylation and defluorination protonation reaction by using o-phosphinophenol photocatalyst
  • Method for defluorination alkylation and defluorination protonation reaction by using o-phosphinophenol photocatalyst
  • Method for defluorination alkylation and defluorination protonation reaction by using o-phosphinophenol photocatalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0096] Example 1, preparation of 2,2-difluoro-6-hydroxyl-N-phenylhexanamide

[0097]

[0098] Following general procedure A, the yields are shown in Table 2.

[0099] The 2,2-difluoro-6-hydroxyl-N-phenylhexanamide obtained in Example 1 was carried out by nuclear magnetic resonance 1 H NMR, 13 C NMR and 19 F NMR analysis.

[0100] Figure 4 is 2,2-difluoro-6-hydroxy-N-phenylhexanamide 1 H NMR spectrum.

[0101] like Figure 4 as shown, 1 H NMR (400MHz, CDCl 3 )δ8.09(s,1H),7.57(d,J=7.9Hz,2H),7.37(t,J=7.9Hz,2H),7.19(t,J=7.4Hz,1H),3.66(t, J=5.7Hz, 2H), 2.32–2.12(m, 2H), 1.73(s, 1H), 1.62(dd, J=7.0, 4.0Hz, 4H).

[0102] Figure 5 is 2,2-difluoro-6-hydroxy-N-phenylhexanamide 13 C NMR spectrum.

[0103] like Figure 5 as shown, 13 C NMR (101MHz, CDCl 3 )δ162.2(t, J=28.6Hz), 136.0, 129.2, 125.6, 120.3, 118.3(t, J=253.6Hz), 62.2, 33.5(t, J=23.2Hz), 31.9, 18.1(t, J = 4.5Hz).

[0104] Image 6 is 2,2-difluoro-6-hydroxy-N-phenylhexanamide 19 F NMR spectrum.

[0105...

Embodiment 2

[0106] Embodiment 2, preparation 2,2-difluoro-6-hydroxyl-N-(4-methoxyphenyl) hexanamide

[0107]

[0108] Following general procedure A, the yields are shown in Table 2.

[0109] The 2,2-difluoro-6-hydroxyl-N-(4-methoxyphenyl) hexanamide obtained in embodiment 2 was carried out by nuclear magnetic resonance 1 H NMR, 13 C NMR and 19 F NMR analysis obtains the result:

[0110] 1 H NMR (400MHz, DMSO) δ10.38(s, 1H), 7.59(d, J=9.1Hz, 2H), 6.93(d, J=9.1Hz, 2H), 3.74(s, 3H), 3.41(t ,J=5.7Hz,2H),2.25–2.04(m,2H),1.52–1.42(m,4H).

[0111] 13 C NMR (101MHz, DMSO) δ162.3(t, J=29.4Hz), 156.8, 130.7, 122.9, 118.7(t, J=251.5Hz), 114.3, 60.7, 55.7, 34.1(t, J=23.3Hz) ,32.2,18.6(t,J=4.3Hz).

[0112] 19 F NMR (376MHz, DMSO) δ-104.1 (2F, t, J=17.3Hz).

Embodiment 3

[0113] Example 3, preparation of 2,2-difluoro-6-hydroxyl-N-(pyridin-3-yl)hexanamide

[0114]

[0115] Following general procedure A, the yields are shown in Table 2.

[0116] The 2,2-difluoro-6-hydroxyl-N-(pyridin-3-yl) hexanamide obtained in embodiment 3 was carried out by nuclear magnetic resonance 1 H NMR, 13 C NMR and 19 F NMR analysis obtains the result:

[0117] 1 H NMR (400MHz, CDCl 3 )δ8.69(s,1H),8.47(s,1H),8.43(d,J=4.4Hz,1H),8.19(d,J=8.4Hz,1H),7.34(dd,J=8.4,4.7 Hz,1H),3.68(t,J=5.7Hz,2H),2.31–2.15(m,2H),1.95(s,1H),1.68–1.60(m,4H).

[0118] 13 C NMR (101MHz, CDCl 3 )δ162.8(t, J=29.5Hz), 146.4, 141.6, 133.3, 127.9, 123.9, 118.1(t, J=253.4Hz), 62.1, 33.5(t, J=23.1Hz), 31.9, 18.1(t ,J=4.4Hz).

[0119] 19 F NMR (376MHz, CDCl 3 )δ-105.2 (2F,td,J=17.3,2.5Hz).

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Abstract

The invention provides a method for defluorination alkylation and defluorination protonation reaction by using an o-phosphinophenol photocatalyst. The method comprises the following steps: providing an o-phosphinophenol photocatalyst, and carrying out photocatalysis on a trifluoromethyl compound (1a) R-CF3 and/or a polyfluoroalkyl compound (1b) R-CF2CF3 in the presence of mercaptan, an alkali, formate and an organic solvent; and reacting with an unsaturated olefin compound (2) to generate a defluorination alkylation product after the defluorination reaction of the trifluoromethyl compound and/or polyfluoroalkyl compound, and reacting with a hydrogen donor to directly generate a defluorination protonation product after defluorination reaction of the trifluoromethyl compound and/or polyfluoroalkyl compound.

Description

technical field [0001] The present disclosure relates to the field of compound synthesis, and in particular, to a method for an o-phosphine phenol photocatalyst for defluoroalkylation and defluorination protonation reactions. Background technique [0002] At present, among the various methods of photocatalytic activation of inert bonds, the direct selection of C-F to activate trifluoromethyl to generate the corresponding difluoromethyl radical is a change of thinking in the synthesis of difluoromethyl-containing compounds, and it is an important method in the pharmaceutical industry. Valuable fluorinated intermediates. Low-cost and readily available trifluoroacetamides, trifluoroacetates, and various trifluoromethylated (hetero)arenes make this transition even more appealing. The widely used photocatalysts in these transformations are noble metal-based polypyridine complexes and π-conjugated organic dyes, which have the disadvantages of high cost and environmental pollution...

Claims

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Application Information

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IPC IPC(8): C07C231/12C07C269/06C07C67/343C07C67/347C07C29/34C07C41/30C07C227/10C07D309/12C07D213/64C07D213/73C07D209/86C07D213/75C07F7/10B01J31/02C07B37/02C07B37/00C07C235/16C07C235/24C07C233/08C07C271/22C07C69/708C07C69/63C07C33/46C07C43/225C07C229/42C07C233/07C07C233/25C07C233/10
CPCC07C231/12C07C269/06C07F7/083C07C67/343C07C67/347C07C29/34C07C41/30C07C227/10C07D309/12C07D213/64C07D213/73C07D209/86C07D213/75C07B37/02C07B37/00B01J35/004B01J31/0267C07C2601/14C07C2601/16B01J2231/32C07C235/16C07C235/24C07C233/08C07C271/22C07C69/708C07C69/63C07C33/46C07C43/225C07C229/42C07C233/07C07C233/25C07C233/10
Inventor 尚睿刘灿张浩
Owner UNIV OF SCI & TECH OF CHINA
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