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Organic catalysts having visible photocatalytic asymmetric hydroxylation photocatalysis performance, and preparation method and application thereof

An organic catalyst, a technology that catalyzes hydroxyl groups. It is applied in the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, etc., and can solve problems such as long reaction time and increased reaction costs.

Active Publication Date: 2018-04-13
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Our research group reported the use of aryloxyamino alcohol catalysts (Tetrahedron.2012,38,7973-7977), diterpene alkaloids (Synlett.2009,16,2659-2662) and quinine derivatives (Adv.Synth.Catal .2016,358,737-745) have good catalytic effect, yet, the method takes a long time to react, and still needs to add organic peroxide as oxidant in the reaction system, which increases the reaction cost

Method used

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  • Organic catalysts having visible photocatalytic asymmetric hydroxylation photocatalysis performance, and preparation method and application thereof
  • Organic catalysts having visible photocatalytic asymmetric hydroxylation photocatalysis performance, and preparation method and application thereof
  • Organic catalysts having visible photocatalytic asymmetric hydroxylation photocatalysis performance, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Preparation of Ia-1a

[0046]

[0047] Weigh 0.767g Cn-1 and 2.12g 5-(4-bromomethylphenyl)-10,15,20-triphenyl-21H,23H-porphyrin (TPP-1) in 50mL CH 2 Cl 2 , under the protection of nitrogen, add 1mL 50% KOH aqueous solution, stir at room temperature for 10 hours, after the reaction is completed, use 50mL water to quench the reaction, and use 3×50mLCH 2 Cl 2 Extraction, drying, spin-drying, crude product column chromatography (MeOH / EA / PE / Et 3 N=5 / 30 / 63 / 2), and 0.524 g of purple solid Ia-1a was obtained with a yield of 38%. 1 H NMR (400MHz, DMSO-d6) δ8.84(s, 4H), 8.72(d, J=4.7Hz, 2H), 8.62(s, 2H), 8.58–8.46(m, 4H), 8.29(m, 3H), 8.21(m, 6H), 8.04(d, J=7.7Hz, 2H), 8.01–7.94(m, 4H), 7.87(m, 9H), 7.74–7.67(m, 1H), 7.59(t ,J=7.4Hz,1H),7.49(t,J=7.7Hz,1H),6.65(s,1H),6.19(d,J=8.5Hz,1H),5.33(d,J=14.3Hz,2H ),5.26–5.17(m,2H),5.09(d,J=11.9Hz,1H),4.67(d,J=12.1Hz,1H),4.37(s,1H),4.02(d,J=15.0Hz ,1H),3.77–3.70(m,1H),3.38(s,2H),2.79–2.65(m,2H),1.81(s,1H),1.46–1.35(m,1H),-2.94(s, ...

Embodiment 2

[0049] Preparation of Ia-2a

[0050]

[0051] Weigh 0.71g of 5-(4-methoxycarbonylphenyl)-10,15,20-triphenyl-21H,23H-porphyrin (TPP-2) and dissolve it in 80mLTHF, add 20mL2MKOH, heat to reflux overnight, cool to room temperature, add 100mL water-extracted aqueous solution containing 5-(4-formylphenyl)-10,15,20-triphenyl-21H,23H-porphyrin potassium salt (TPP-3), the water phase is not Post-processing proceeds directly to the next step.

[0052] Add 0.77g Cn-1 and 200mL CHCl to the aqueous solution containing TPP-3 3 , stirred at room temperature for 1 h, separated and collected the organic phase, washed the organic phase with 3×50 mL of water, dried, and rotary evaporated to obtain 1.31 g of purple solid Ia-2a with a yield of 97%. 1 H NMR (400MHz, DMSO-d6) δ8.82 (s, 8H), 8.54 (d, J = 8.6Hz, 3H), 8.39 (s, 1H), 8.19 (d, J = 15.8Hz, 12H), 7.94 (d,J=18.6Hz,5H),7.82(s,10H),7.06(s,1H),6.91(s,2H),6.61(s,1H),5.17(d,J=12.1Hz,1H) ,5.04(d,J=12.6Hz,1H),4.44(s,1H),3.98(s,2H),3.73(m,1H...

Embodiment 3

[0054] Preparation of Ia-3a

[0055]

[0056] Weigh 0.75gCn-3, 1.78gTPP-4 and 0.55gK 2 CO 3 and 0.12gPd(PPh 3 ) 4 in 50mLMeOH and 75mLPhCH 3 , under the protection of nitrogen, heated to 80 ° C, the reaction 12h. Cool to room temperature, add 200mL CH 2 Cl 2 , using 200mL10%Na 2 CO 3 Solution washing and 3×50mL water washing, organic phase using anhydrous Na 2 SO 4 Drying, rotary evaporation, the crude product was separated by column chromatography (MeOH / CH 2 Cl 2 =1 / 20), to obtain 1.27g purple solid Cn-4, yield 70%. 1 H NMR (400MHz, DMSO-d6) δ8.95(d, J=4.8Hz, 2H), 8.83(d, J=9.7Hz, 6H), 8.70(d, J=7.9Hz, 2H), 8.53(d ,J=9.3Hz,2H),8.41(d,J=7.8Hz,2H),8.28–8.15(m,7H),7.92–7.70(m,11H),6.55(m,3H),3.69(s, 1H), 3.13(s, 1H), 1.87(s, 1H), 1.75(s, 2H), 1.58(m, 2H), 1.37–1.27(m, 2H), 1.14(t, J=7.5Hz, 5H ),0.88(t,J=7.3Hz,3H),0.79(t,J=7.2Hz,2H),-2.91(s,2H).

[0057] Weigh 0.636g Cn-4 and 0.276g 3,5-dibromobenzyl bromide in 10mLTHF, heat to reflux, react overnight, cool to ...

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Abstract

The invention belongs to the technical field of visible photocatalytic asymmetric organic synthesis, and provides organic catalysts having a visible photocatalytic asymmetric hydroxylation photocatalysis performance, and a preparation method and an application thereof. The catalysts are organic catalysts having a visible photocatalytic asymmetric hydroxylation performance, constructed through combining an asymmetric organic catalyst with a visible photosensitizer through chemical bonds. The catalysts successfully realize the formation of an asymmetric C-O bond through catalytic activation of aC-H bond with molecular oxygen as an oxidizer. The invention especially relates to a most concise method for catalyzing the asymmetric alpha-hydroxylation reaction of a beta-dicarbonyl compound to prepare an alpha-chiral hydroxyl-beta-dicarbonyl compound. The method has the advantages of mild reaction conditions, good substrate applicability and environmental protection. The catalysts have the advantages of extreme easiness in separation from the substrate, stable performances, realization of keeping the catalysis effect after multi-time cycle use, and good application and development values.

Description

technical field [0001] The invention belongs to the technical field of visible light catalysis asymmetric organic synthesis, and relates to a class of organic catalysts with visible light catalysis asymmetric hydroxylation performance. Background technique [0002] Light, as a clean and renewable energy source, makes the use of visible light to catalyze asymmetric reactions a current research hotspot. In the past ten years, organometallic catalytic and organocatalytic systems have been gradually developed and applied in asymmetric alkylation, free radical cross-coupling, dehydrogenation coupling, redox and other systems. In 2004, Córdova first reported the use of photocatalytic asymmetric oxidation reaction. Under ultraviolet light, TPP activated molecular oxygen to make 3 o 2 activated into 1 o 2 , to achieve asymmetric α-oxidation of aldehydes. The reaction requires ultraviolet light, and a photosensitizer and a chiral catalyst are added separately at the same time. ...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07D487/22C07C67/31C07C231/12C07C69/757C07C235/82
CPCC07C67/31C07C231/12C07D487/22B01J31/0244B01J31/0258C07B41/02B01J2231/40B01J35/39C07C69/757C07C235/82
Inventor 孟庆伟唐晓飞刘广志都健冯世豪武玉峰尹航
Owner DALIAN UNIV OF TECH
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