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Carbohydrate alkyl bonding imidazole type heterocyclic carbene palladium coordination compound as well as preparation method and application thereof

A carbohydrate and alkyl bond technology, applied in the field of synthesis and catalysis of chiral nitrogen heterocyclic carbene transition metal complexes, can solve the problems of increasing complexity, violating the principle of environmental protection, atom economy, reducing the total yield of the reaction, etc. problems, to achieve the effects of convenient post-treatment, good substrate universality and functional group tolerance, good catalytic activity and reaction selectivity

Inactive Publication Date: 2018-09-28
GANNAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

A series of ligands based on glucose-derived chiral NHCs have been reported and used in palladium (Pd)-catalyzed Suzuki coupling reactions. All current methods on glucose-derived chiral NHCs-Pd complexes are two-step methods, starting with imidazolium Salt and Ag 2 O reaction to prepare Ag-NHCs complexes, and then Ag-NHCs complexes react with palladium salts to synthesize NHCs-Pd complexes by NHCs transfer method, which not only increases the complexity, but also violates the principles of environmental protection and atom economy. At the same time, it also reduces the overall yield of the reaction, such as C-6 bonded chiral NHCs-Pd on the glucose ring for Suzuki coupling [Organometallics 2010,29,5959-5971], C-1 and C- 3-bonded sugar-containing chiral NHCs transition metal complexes and catalytic activities have also been reported, but their preparations are two-step synthesis [Eur.J.Inorg.Chem.2007,2007,2221-2224; J.Organomet .Chem.2007, 692, 4593-4602; Organometallics 2007, 26, 1126-1128; Organometallics 2010, 29, 403-408; DaltonTrans.2011, 40, 4826-4829; .Chem.Soc.Jpn.2017,90(1),59-67; Bull.Chem.Soc.Jpn.2017,90(9),1050-1057]

Method used

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  • Carbohydrate alkyl bonding imidazole type heterocyclic carbene palladium coordination compound as well as preparation method and application thereof
  • Carbohydrate alkyl bonding imidazole type heterocyclic carbene palladium coordination compound as well as preparation method and application thereof
  • Carbohydrate alkyl bonding imidazole type heterocyclic carbene palladium coordination compound as well as preparation method and application thereof

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Experimental program
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Embodiment 1

[0030] This embodiment relates to a one-step preparation method of a carbohydrate alkyl-linked imidazole-type azacyclic carbene palladium complex, which includes the following steps:

[0031] Under nitrogen protection, 1.0 mmol brominated 1-[2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy )-ethyl]-3-methylimidazolium salt, 1.0mmol of palladium acetate, 3.0mmol of dry pyridine, vigorously reflux reaction in 10mL of dry THF for 4 hours, thin-layer chromatography tracking (methylene chloride:methanol=20:1 ), after the reaction was complete, stop the reaction, post-treatment, column chromatography purification (methylene chloride: methanol = 20: 1), to obtain yellow viscous compound I-1, yield 95%, 1 H NMR (400MHz, CDCl 3)δ1.97(s,3H),1.99(s,3H),2.00(s,3H),2.04(s,2H),2.08(s,3H),3.70(m,1H),4.08(s,3H ),4.12(m,2H), 4.25(dd,J 1 =12.0Hz,J 2 =4.8Hz, 1H), 4.33(m, 3H), 4.52(d, J=8.0Hz, 2H), 4.98(m, 2H).5.06(t, J=14.0Hz, 1H), 5.16(t, J =9.2Hz,1H),6.86(d,J=2.0Hz,1H),6.98(d,J=2.3Hz,1H),7...

Embodiment 2

[0034] This embodiment relates to a method for preparing a carbohydrate alkyl-linked imidazole-type azacyclic carbene palladium complex, which comprises the following steps:

[0035] Add 1.0 mmol of brominated 1-[2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-ethyl ]-3-butyl imidazolium salt, palladium acetate of 1.0mmol, dry pyridine of 3.0mmol, violent reflux reaction in 10mL dry THF 4 hours, thin-layer chromatographic tracking (dichloromethane:methanol=20:1), reaction is complete Afterwards, stop the reaction, work up, and purify by column chromatography (dichloromethane:methanol=20:1) to obtain yellow viscous compound I-2 with a yield of 93%. 1 H NMR (400MHz, CDCl 3 )δ1.01(t, J=7.6Hz, 3H), 1.23 (t, J=7.2Hz, 4H), 1.46(m, 2H), 1.94(s, 3H), 1.97(s, 3H), 1.99( s,3H),2.02(s,3H), 2.07(s,3H),3.69(m,1H),4.10(m,2H),4.23(m,1H),4.29(m,1H),4.42(m ,3H),4.52(m,2H),4.98(m,2H).5.05(t,J=10.0Hz,1H),5.15(t,J=9.2Hz,1H),6.87(d,J=6.0Hz ,1H),6.98(d,J=2.0Hz,1H),7.32(m,2H),7.75(m,1H),8.99(m,...

Embodiment 3

[0038] This embodiment relates to a method for preparing a carbohydrate alkyl-linked imidazole-type azacyclic carbene palladium complex, which comprises the following steps:

[0039] Add 1.0 mmol of brominated 1-[2-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-ethyl ]-3-phenylimidazolium salt, palladium acetate of 1.0mmol, dry pyridine of 3.0mmol, violent reflux reaction in 10mL dry THF 4 hours, thin-layer chromatographic tracking (dichloromethane:methanol=20:1), reaction is complete Afterwards, the reaction was stopped, after-treatment, and column chromatography purification (dichloromethane:methanol=20:1) to obtain yellow viscous compound I-3 with a yield of 91%; 1 H NMR (400MHz, CDCl 3 )δ2.00(s,3H),2.01(s,3H), 2.02(s,3H),2.04(s,3H),2.09(s,3H),3.72(m,1H),4.10(m,3H ),4.28(m,1H),4.41(m,1H),4.52(m,2H),4.59(d,J=8.0Hz,2H).5.05(t,J=10.0Hz,1H),5.12(t ,J=10.0Hz,1H),5.19(t,J=8.8Hz,1H),7.14(d,J=2.0Hz,1H),7.18(d,J=2.4Hz,1H), 7.26(m,2H ),7.48(m,1H),7.58(t,J=8.0Hz,2H),7.70(m,1H),8.8...

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Abstract

The invention provides a carbohydrate alkyl bonding imidazole type N-heterocyclic carbene palladium coordination compound as well as a preparation method and application thereof. A structure of the carbohydrate alkyl bonding imidazole type N-heterocyclic carbene palladium coordination compound is shown in a formula I: the formula (1) is shown in the description, wherein R is alkyl, benzyl or aryl,and n is equal to 2 to 10. According to the carbohydrate alkyl bonding imidazole type N-heterocyclic carbene palladium coordination compound disclosed by the invention, by using natural chiral compound D-glucose with low cost, easy availability, good water solubility and rich stereochemistry as a chiral source of the carbohydrate alkyl bonding imidazole type N-heterocyclic carbene palladium coordination compound, under a condition of no additional addition of an alkaline additive, a carbohydrate alkyl bonding imidazole type N-heterocyclic carbene palladium complex I is synthesized by adoptinga quick one-step method and is used as a palladium catalyst for catalyzing C-C coupled reaction, and no-water no-oxygen reaction conditions are overcome, so that a series of fluorene-derived conjugated small molecular functional materials having novel structures are prepared in a high yield manner.

Description

technical field [0001] The invention relates to a carbohydrate alkyl-linked imidazole-type azacyclic carbene palladium complex, a preparation method and application thereof, and belongs to the field of synthesis and catalysis of chiral azacyclic carbene transition metal complexes. Background technique [0002] Transition metal catalyzed reactions are an important means of modern organic chemistry, especially the outstanding contribution of palladium catalysts in C-C coupling reactions, so that the 2010 Nobel Prize in Chemistry was awarded to chemists Suzuki, Heck and Negishi who have made significant contributions to the field of palladium catalysis . [0003] Carbohydrates are suitable screening pools for chiral skeletons. Since Arduengo first isolated stable N-heterocyclic carbenes (NHCs) in 1991, people have increasingly Focus on NHCs as auxiliary ligands and catalysts, especially NHCs-coordinated palladium catalysts have received the most extensive attention. It is well...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07H23/00B01J31/22C07D333/76C07C41/30C07C43/205C07D317/50C07C17/263C07C25/22
CPCB01J31/22B01J2231/4211B01J2531/824C07C17/263C07C41/30C07C2603/18C07D317/50C07H23/00C07C43/2055C07C25/22
Inventor 周中高元洋洋刘光胜徐国海李梅谢永荣
Owner GANNAN NORMAL UNIV
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