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Biphenyl nitrone carbocyclic carbene-palladium complex and method for synthesizing same

A technology of biphenyl nitrone and a synthesis method is applied in the field of α-biphenyl nitrone carbocyclic carbene-palladium complex and its synthesis, and can solve the problems of difficulty in purifying reaction operation products and the like

Inactive Publication Date: 2008-08-27
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, when using this type of catalyst to catalyze the Heck reaction, it needs to be carried out under anhydrous and oxygen-free conditions, and there are 10% regioisomers in the product, which brings difficulties to the reaction operation and product purification.

Method used

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  • Biphenyl nitrone carbocyclic carbene-palladium complex and method for synthesizing same
  • Biphenyl nitrone carbocyclic carbene-palladium complex and method for synthesizing same
  • Biphenyl nitrone carbocyclic carbene-palladium complex and method for synthesizing same

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Dissolve α-[2-(4-methoxyphenyl)]phenyl-N-tert-butylnitrone (142 mg, 0.5 mmol) and palladium diacetate (113 mg, 0.5 mmol) in glacial acetic acid (2mL ), the reaction was refluxed for 10 hours. After the reaction, the solvent was removed under reduced pressure, and then separated and purified by silica gel column chromatography to obtain the α-biphenone carbene-palladium complex of structural formula (III).

[0040]

[0041] Formula (III)

[0042] In the formula, R is p-methoxy.

[0043] When silica gel column chromatography is used for separation and purification, first eluted with ethyl acetate / petroleum ether = 1 / 4 to remove impurities, and then eluted the product with ethanol.

[0044] The yield of the α-biphenylnitrocarbene-palladium complex was 74%. Mp: 176-178°C; a mixture of trans and cis isomers (trans / cis=77 / 23); 1 H NMR(400MHz, CDCl 3 ): Anti-isomer (major): δ7.68(s, 2H), 7.47(d, J=7.6Hz, 2H), 7.05-7.77(m, 12H), 3.87(s, 6H), 2.09( s, 6H), 1.02 (s, 18H); cis-isome...

Embodiment 2

[0046] The synthesis method is the same as in Example 1, except that α-[3-(4-methoxyphenyl)]phenyl-N-tert-butylnitrone is used instead of α-[2-(4-methoxyphenyl) ]Phenyl-N-tert-butylnitrone. Obtain the α-bifenone carbene-palladium complex of structural formula (IV),

[0047]

[0048] Formula (IV)

[0049] In the formula, R is p-methoxy.

[0050] The yield of the α-biphenylnitrocarbene-palladium complex was 56%. Mp: 170-172°C; a mixture of trans and cis isomers (trans / cis=91 / 9); 1H NMR(400MHz, CDCl 3 ): Anti-isomer (major): δ 7.53 (d, J = 8.4 Hz, 2H), 7.51 (s, 2H), 7.43 (d, J = 8.4 Hz, 4H), 7.27 (d, J = 8.4Hz, 2H), 7.11 (s, 2H), 6.95 (d, J=8.4Hz, 4H), 3.84 (s, 6H), 2.12 (s, 6H), 1.14 (s, 18H); cis-isomer Body (minor, selected peak): 1.51 (s, 18H); 13 C NMR(100MHz, CDCl 3 ): Anti-isomer δ180.8, 158.9, 138.1, 136.7(x2), 134.8, 132.8, 127.5(x2), 126.8(x2), 125.3, 114.2(x 2), 69.5, 55.3, 27.9(x 3 ), 24.3. cis-isomer (minor, selected peaks) 127.7(×2), 114.1(×2), 28.3(×3).

Embodiment 3

[0052] The synthesis method is the same as in Example 1, the difference is that α-[4-(4-methoxyphenyl)]phenyl-N-tert-butylnitrone is used instead of α-[2-(4-methoxyphenyl) ] Phenyl-N-tert-butyl nitrone was refluxed in 5 mL of glacial acetic acid for 5 hours to obtain the α-biphenyl nitro carbene-palladium complex of structural formula (V),

[0053]

[0054] Formula (V)

[0055] In the formula, R is p-methoxy.

[0056] The yield is 60%. Mp: 174-176°C; a mixture of trans and cis isomers (trans / cis=90 / 10);

[0057] 1 H NMR(400MHz, CDCl 3 ): Anti-isomer (major): δ7.71(s, 2H), 7.54(d, J=8.4Hz, 4H), 7.46(s, 2H), 7.22(d, J=7.6Hz, 2H) , 7.01 (d, J = 7.6 Hz, 2H), 6.96 (d, J = 8.4 Hz, 4H), 3.85 (s, 6H), 2.12 (s, 6H), 1.05 (s, 18H); cis-isomer Body (minor, selected peaks): 1.49 (s, 18H); 13 C NMR(100MHz, CDCl 3 ): Anti-isomer (major): δ180.7, 159.3, 139.7, 138.4, 137.8, 133.2, 132.0, 129.1, 128.1 (x2), 123.7, 122.5, 114.1 (x2), 69.1, 55.3, 27.7 (x 3), 24.3. cis-isomer (minor, selected peak...

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Abstract

The invention discloses an alpha-biphenyl nitrone homocycle carbene-palladium complex, represented as formula (I). The synthesis method comprises adding alpha-biphenyl nitrone compound and palladium diacetic acid of same equivalent into acetic acid, refluxing and reacting for 5-10h, separating and purifying to obtain the product. The alpha-biphenyl nitrone homocycle carbene-palladium complex can effectively catalyze Heck reaction and Suzuki coupling reaction.

Description

Technical field [0001] The invention relates to an α-biphenylnitrone-based carbocyclic carbene-palladium complex as a catalyst for Heck reaction and Suzuki coupling reaction and a synthesis method thereof. Background technique [0002] The formation of CC bonds between unsaturated carbons plays a very important role in organic synthesis, such as the synthesis of drugs, materials, optical devices, etc. The Heck reaction and Suzuki coupling reaction are both important methods for the formation of CC bonds. It is widely used in organic synthesis. The Heck reaction is the arylation reaction of halogenated aromatic hydrocarbons to olefins, and the Suzuki coupling reaction is the coupling reaction of alkenyl or aryl boron reagents and unsaturated halogenated reagents, both of which need to be completed under palladium catalysis. In the Heck reaction and Suzuki coupling reaction, the ligand plays a key role in the catalytic activity of the palladium catalyst. Therefore, in order to impr...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/22B01J31/28
Inventor 吴金龙戴静戴伟民
Owner ZHEJIANG UNIV
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