A kind of tridentate carbene and its preparation method and application

Abstract

The present invention provides a kind of tridentate carbene and its preparation method and application, tridentate carbene has the structure of formula [1], wherein, R 1 and R 2 independently selected from substituted or unsubstituted C 1－10 Alkanes, C 3－10 Cycloalkyl, C 2－10 Alkenyl, C 2－10 Alkynyl, aryl. It has strong catalytic performance, can be used as a catalyst in various reactions, and the preparation method is simple and feasible.

Description

technical field

[0001] The invention relates to a tridentate carbene and its preparation method and application, belonging to the technical field of organic catalysis. Background technique

[0002] Since N-heterocyclic carbene is similar to electron-rich phosphine ligands, and metal carbene bonds have good thermal stability, water resistance and oxidation resistance, N-heterocyclic carbene can replace unstable The use of phosphine ligands in catalytic reactions has attracted widespread attention from scientists.

[0003] In 1995, Herrmann et al. first reported the application of N-heterocyclic carbene transition metal compounds in catalytic reactions, and realized that this type of metal compounds had superior catalytic properties. Since then, N-heterocyclic carbene has been rapidly developed in the field of organometallic synthesis and homogeneous catalysis, and has become one of the research hotspots in the field of organic chemistry.

[0004] However, there are no repor...

Examples

Embodiment 1

[0087] The present embodiment prepares the compound shown in formula [a], comprises the following steps:

[0088] 1) 1,3-bis(1,3-bis(2,6-diisopropyl-benzene)-1,2,3-triazole)-dimethylamine salt (L 2 ) preparation

[0089] Add potassium hexafluorophosphate (1.9g, 10.4mmol) into a 250mL schlenk bottle, heat and pump for N 2 Several times, add 1,3-bis(2,6-diisopropyl-benzene)-triazene (5.0 g, 13.4 mmol) after the schelenk bottle is cooled, and ventilate three times, then cool down to -78 ° C, Add 50 mL of ultra-dry dichloromethane, add BOC-protected dipropynylamine (10 g, 5.2 mmol), and after the temperature is stabilized at -78 ° C, protect from light, add t BuOCl (1.30mL, 11.4mmol), heated by itself overnight. Suction filter in a ventilated place, wash the solid with dichloromethane, collect the filtrate, and remove the dichloromethane by rotary evaporation to obtain a white solid. Then add 100mL diethyl ether to wash to obtain white solid L 1 3.98 g, yield: 63%.

[0090]...

Embodiment 2

[0101] Compound shown in the present embodiment preparation formula [b]

[0102] In Example 1, 1,3-bis(2,6-diisopropyl-benzene)-triazene was replaced by 1,3-bis(2,4,6-trimethyl-benzene)-tri Nitrogen, the rest of the conditions are the same as in Example 1 to obtain the compound shown in formula [b].

[0103] The compound shown in the formula [b] prepared in embodiment 2 can be passed through proton nuclear magnetic resonance spectrum ( 1 (HNMR) test to verify its structure, characterized as follows:

[0104] 1 HNMR (CDCl 3 ,400MHz,δppm)δ7.06(s,4H),7.05(s,4H),4.00(s,4H),2.36(d,J=2.4Hz,12H),2.15(s,12H),2.09(s ,12H).

Embodiment 3

[0106] The present embodiment prepares the compound shown in formula [c], comprises the following steps:

[0107] 1) L 4 preparation of

[0108] DMSO:H in an oven-dried 100 mL schlenk bottle 2 O (9:1) mixed solution was added with 1-phenyl-azidobenzene (0.68g, 5.7mmol) and cuprous iodide (0.099g, 0.5mmol) and stirred for 10 minutes. BOC-protected dipropynylamine (0.5 g, 2.6 mmol) was added and stirred for another 24 hours, the reaction mixture was added to ice water, a solid precipitated out, the solvent was filtered off, the precipitate was washed with water and acetone, and dried under vacuum to obtain a white solid L 3 0.98g, Yield: 87%.

[0109] Add L to the dried 100mL schlenk bottle 3 (86.3mg, 0.2mmol), and added 5mL of ultra-dry dichloromethane, cooled to -78°C, then added methyl trifluoromethanesulfonate (72.2mg, 0.44mmol), when the reaction rose to room temperature, added trifluoromethane Sulfonic acid (75.0mg, 0.50mmol) was extracted with dichloromethane after ...

technical field

[0001] The invention relates to a tridentate carbene and its preparation method and application, belonging to the technical field of organic catalysis. Background technique

[0002] Since N-heterocyclic carbene is similar to electron-rich phosphine ligands, and metal carbene bonds have good thermal stability, water resistance and oxidation resistance, N-heterocyclic carbene can replace unstable The use of phosphine ligands in catalytic reactions has attracted widespread attention from scientists.

[0003] In 1995, Herrmann et al. first reported the application of N-heterocyclic carbene transition metal compounds in catalytic reactions, and realized that this type of metal compounds had superior catalytic properties. Since then, N-heterocyclic carbene has been rapidly developed in the field of organometallic synthesis and homogeneous catalysis, and has become one of the research hotspots in the field of organic chemistry.

[0004] However, there are no repor...

Examples

Embodiment 1

[0087] The present embodiment prepares the compound shown in formula [a], comprises the following steps:

[0088] 1) 1,3-bis(1,3-bis(2,6-diisopropyl-benzene)-1,2,3-triazole)-dimethylamine salt (L 2 ) preparation

[0089] Add potassium hexafluorophosphate (1.9g, 10.4mmol) into a 250mL schlenk bottle, heat and pump for N 2 Several times, add 1,3-bis(2,6-diisopropyl-benzene)-triazene (5.0 g, 13.4 mmol) after the schelenk bottle is cooled, and ventilate three times, then cool down to -78 ° C, Add 50 mL of ultra-dry dichloromethane, add BOC-protected dipropynylamine (10 g, 5.2 mmol), and after the temperature is stabilized at -78 ° C, protect from light, add t BuOCl (1.30mL, 11.4mmol), heated by itself overnight. Suction filter in a ventilated place, wash the solid with dichloromethane, collect the filtrate, and remove the dichloromethane by rotary evaporation to obtain a white solid. Then add 100mL diethyl ether to wash to obtain white solid L 1 3.98 g, yield: 63%.

[0090]...

Embodiment 2

[0101] Compound shown in the present embodiment preparation formula [b]

[0102] In Example 1, 1,3-bis(2,6-diisopropyl-benzene)-triazene was replaced by 1,3-bis(2,4,6-trimethyl-benzene)-tri Nitrogen, the rest of the conditions are the same as in Example 1 to obtain the compound shown in formula [b].

[0103] The compound shown in the formula [b] prepared in embodiment 2 can be passed through proton nuclear magnetic resonance spectrum ( 1 (HNMR) test to verify its structure, characterized as follows:

[0104] 1 HNMR (CDCl 3 ,400MHz,δppm)δ7.06(s,4H),7.05(s,4H),4.00(s,4H),2.36(d,J=2.4Hz,12H),2.15(s,12H),2.09(s ,12H).

Embodiment 3

[0106] The present embodiment prepares the compound shown in formula [c], comprises the following steps:

[0107] 1) L 4 preparation of

[0108] DMSO:H in an oven-dried 100 mL schlenk bottle 2 O (9:1) mixed solution was added with 1-phenyl-azidobenzene (0.68g, 5.7mmol) and cuprous iodide (0.099g, 0.5mmol) and stirred for 10 minutes. BOC-protected dipropynylamine (0.5 g, 2.6 mmol) was added and stirred for another 24 hours, the reaction mixture was added to ice water, a solid precipitated out, the solvent was filtered off, the precipitate was washed with water and acetone, and dried under vacuum to obtain a white solid L 3 0.98g, Yield: 87%.

[0109] Add L to the dried 100mL schlenk bottle 3 (86.3mg, 0.2mmol), and added 5mL of ultra-dry dichloromethane, cooled to -78°C, then added methyl trifluoromethanesulfonate (72.2mg, 0.44mmol), when the reaction rose to room temperature, added trifluoromethane Sulfonic acid (75.0mg, 0.50mmol) was extracted with dichloromethane after ...

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