CN104744519B - Ring expansion N-heterocyclic carbine palladium compound containing picolyl - Google Patents

Ring expansion N-heterocyclic carbine palladium compound containing picolyl Download PDF

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CN104744519B
CN104744519B CN201510107498.6A CN201510107498A CN104744519B CN 104744519 B CN104744519 B CN 104744519B CN 201510107498 A CN201510107498 A CN 201510107498A CN 104744519 B CN104744519 B CN 104744519B
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room temperature
ring expansion
heterocyclic carbine
palladium compound
picolyl
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CN104744519A (en
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杨亮茹
买文鹏
毛璞
肖咏梅
袁金伟
屈凌波
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Henan University of Technology
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Abstract

The invention belongs to organic compound field, it is related to pincerlike ring expansion N-heterocyclic carbine palladium compound.The compound has following structure：

Description

Ring expansion N-heterocyclic carbine palladium compound containing picolyl
Technical field
The invention belongs to organic compound field, it is related to pincerlike ring expansion N-heterocyclic carbine palladium compound and its in catalysis C-N Application in coupling reaction.
Background technology
It is organic that N-heterocyclic carbine (N-Heterocyclic Carbenes, NHCs) and its metallic compound are used for metal Chemistry, Coordinative Chemistry, homogeneous catalysis, materials chemistry and field of pharmaceutical chemistry research.Research focuses mostly in five yuan of azepines at present Ring Cabbeen (five yuan of-NHCs) and its metallic compound, include classic imidazoles -2- carbine metals compound, the miaow of imidazole derivatives Oxazoline -2- carbine metals compound (A-D) and Crabtree professor seminar report first using imidazoles -4- Cabbeens as representative Non-classical type carbine metal compound (E-F).
Five yuan of-NHCs- metallic compounds of imidazole derivatives
Connecting on the pincerlike nitrogen heterocycle carbine ligand of three teeth, i.e., the Cabbeen carbon, Ν in part in substituent has coordination work( The hetero atom of energy, is coordinated with same metal center, forms the complex with cyclic structure.In addition, nitrogen heterocycle carbine ligand sheet Body also have stronger σ-coordination ability, thus three teeth pincerlike penta azacyclo carbine metal compound under normal circumstances to sky The stability enhancing of gas and water point and heat, is conducive to it to prepare and apply, achieved in terms of homogeneous catalysis widely should With.For example, the pincerlike five yuan-N-heterocyclic carbine palladium compound of PCP, NCN, CCC, CNC of tridentate ligand be widely used in Heck, The C-C such as Suzuki coupling reactions (bibliography (a) Liao, C.-Y.；Chan,K.–T.；Zeng,J.–Y.；Hu,C.–H.；Tu, C.–Y.；Lee,H.M.Organometallics 2007,26,1692.(b)Hahn,F.E.；Jahnke,M.C.；Pape, T.Organometallics 2006,25,5927.(c)Lee,H.M.；Zeng,J.Y.；Hu,C.–H.；Lee,M.– T.Inorg.Chem.2004,43,6822.(d)Tsoureas,N.；Danopoulos,A.A.；Tulloch,A.A.D.； Light,M.E.Organometallics 2003,22,4750.(e)Herrmann,W.A.；V.P.W.；C.W.K.；Grosche,M.；Reisinger,C.–P.；Weskamp,T.J.Organomet.Chem.2001, 617-618,616.(f)Yang,C.；Lee,H.M.；Nolan,S.P.Org.Lett.2001,3,1511.).
The C-C coupling reactions of pincerlike NHC-Pd compound for catalysis
NHCs of the atom number more than five is referred to as ring expansion N-heterocyclic carbine (Ring-Expanded NHCs, RE- on heterocycle NHCs), compared with five yuan of-NHCs, it is hexa-atomic-, seven yuan-etc. RE-NHCs show significantly different property, especially significantly increase Alkalescence/nucleophilicity and three-dimensional effect, thus the architectural feature of respective metal compound, catalytic activity and selectivity are substantially not yet Together.Due to σ-electron supplying capacity enhancing of ring expansion N-heterocyclic carbine, N-Ccarbene-N bond angles become big, R-N-Ccarbene bond angles Diminish, promote substituent on N closer to metal center, to increase steric effect, so as to improve the active of catalyst and stably Property.Structure (bibliography (a) Collins, L.R. as follows for the ring expansion N-heterocyclic carbine metal compound reported； Rookes,T.M.；Mahon,M.F.；Riddlestone,I.M.；Whittlesey,M.K.Organometallics 2014, 33,5882.(b)Dunsford,J.J.；Cavell,K.J.；Kariuki,B.M.Organometallics 2012,31, 4118.(c)Park,J.K.；Lackey,H.H.；Ondrusek,B.A.；McQuade,D.T.J.Am.Chem.Soc.2011, 133,2410.(d)Armstrong,R.；Ecott,C.；Mas-Marzá,E.；Page,M.J.；Mahon,M.F.； Whittlesey,M.K.Organometallics 2010,29,991.(e)Scarborough,C.C.；Grady,M.J.W.； Guzei,I.A.；Gandhi,B.A.；Bunel,E.E.；Stahl,S.S.Angew.Chem.,Int.Ed.2005,44,5269.
The part of document report is hexa-atomic-, seven yuan-, etc. RE-NHCs- metallic compounds
At present, in the synthesis of RE-NHCs and its metallic compound and the document report of performance, the card in N-heterocyclic carbine Guest's carbon and metal-complexing, form the simple complex compound of monodentate ligand, and catalytic effect is not ideal.Explore new pincerlike ring expansion azepine Ring carbine metal catalyst, is conducive to the synthesis of the C-N coupling reaction aromatic amine compounds of palladium chtalyst.The pincers of current tridentate ligand Shape ring expansion N-heterocyclic carbine metal compound has no report.
The content of the invention
It is an object of the invention to provide the pincerlike ring expansion N-heterocyclic carbine palladium compound of the tridentate ligand of excellent catalytic effect.
Pincerlike ring expansion N-heterocyclic carbine palladium compound of the present invention has below general formula：
R is simultaneously identical or different；X is simultaneously identical or different.
The following compound of preferred structure：
Above-claimed cpd synthetic route is as follows：
The synthetic method of pincerlike ring expansion N-heterocyclic carbine palladium compound of the present invention is achieved by the steps of：
(1) 1,3- propane diamine derivative and 2- pyridine carboxaldehyde derivatives are with 1:2 mol ratios, in methyl alcohol, successively through dehydration, Reduce to obtain disubstituted 1,3- propane diamine derivative；Cyclization further occurs in methyl alcohol with the formalin of equimolar amounts anti- Should, generate hexahydropyrimidine derivative；
(2) hexahydropyrimidine derivative and NBS are with 1:1 mol ratio, dehydrogenation is reacted in glycol dimethyl ether, generates tetrahydropyrimidine After bromide derivative, anion exchange occurs in ethanol with the ammonium hexafluorophosphate of 1.5 moles, tetrahydropyrimidine hexafluoro is generated Phosphate；
(3) tetrahydropyrimidine hexafluorophosphate and palladium bichloride are with 1:0.5-2 mol ratios, in organic solvent, alkali exist Under, at a temperature of 50~200 DEG C, react 5~25 hours, after removal of solvent under reduced pressure, cross the ring expansion azepine that post separation obtains pincer Ring carbene-palladium compound.
1,3 propane diamine derivative of the present invention is 1,3- propane diamine, 2,2- dimethyl -1,3- propane diamine；Described 2- pyridine carboxaldehydes derivative is 2- pyridine carboxaldehydes, 5- bromo-2-pyridyls formaldehyde, 6- bromo-2-pyridyl formaldehyde.
Organic solvent of the present invention is tetrahydrofuran, toluene, 1,4- dioxane, pyridine, N, N- dimethyl formyls Amine, dimethyl acetamide, 1-METHYLPYRROLIDONE, glycol dimethyl ether, dimethyl sulfoxide (DMSO).
Alkali of the present invention is double (trimethylsilyl) Sodamide, double (trimethylsilyl) potassamides, tert-butyl alcohols Sodium, potassium tert-butoxide, sodium tert-amyl alcohol, tert-pentyl alcohol potassium.
The pincerlike ring expansion N-heterocyclic carbine palladium compound that the present invention is synthesized has unique design feature, under microwave radiation Show efficient catalytic performance to the C-N coupling reactions of bromobenzene, heterocycle halogenated aryl hydrocarbon and amine, arylamine be common in drug molecule and It is also the important feature unit of many new function materials in natural products.The C-N coupling reactions of palladium chtalyst are synthesizing arylamines A kind of important method of compound.The compounds of this invention provides a class new metallic catalyst for C-N coupling reactions, for urging When changing C-N coupling reactions, the reaction time is short, and catalyst amount is few, need not be handled, grasped using alkali cheap and easy to get, reaction dissolvent Make simple, catalysis yield high.
Catalysis C-N coupling reactions use following steps：By ring expansion N-heterocyclic carbine palladium compound catalyst of the invention pincerlike, Alkali, halogenated aryl hydrocarbon, amine are added in solvent, under microwave radiation after 50~100 DEG C are reacted 10~40 minutes, are down to room temperature, Removal of solvent under reduced pressure, pillar layer separation obtains sterling.
Embodiment
Below in conjunction with preferred embodiments, the present invention is described further, but protection scope of the present invention is not limited in This：
Embodiment 1
In 100mL round-bottomed flasks, by pyridine-2-formaldehyde (30mmol, 3.21g) and 1,3- propane diamine (15mmol, 1.11g) mixed in 30mL methanol, after reacting at room temperature 5.0 hours, NaBH is slowly added under ice-water bath stirring4(120mmol, 4.54g), 70 DEG C are slowly ramped to react 5 hours, room temperature is cooled to, is spin-dried for reaction solution.50mL CH are used again2Cl2Dissolving, filtering, Filtrate is spin-dried for, and must remain yellow oily dope.Above-mentioned yellow oily dope is dissolved in after 30mL methanol, add thereto etc. Mole formalin, is stirred at room temperature after 3 hours, removal of solvent under reduced pressure, and column chromatographic isolation and purification obtains (the 2- pyridine first of 1,3- bis- Base) hexahydropyrimidine (3.50g, yield 87%).
In 100mL round-bottomed flasks, (2- picolyls) hexahydropyrimidines of 1,3- bis- (5mmol, 1.34g) are dissolved in 30mL second Glycol dimethyl ether (DME), adds N- bromo-succinimides (NBS, 5mmol, 0.89g), is stirred at room temperature after 3 hours thereto, Suction filtration, faint yellow filter cake is recrystallized through dichloromethane-ether, obtains 1,3- bis- (2- picolyls) tetrahydropyrimidine bromide pure Product.The ammonium hexafluorophosphate of (2- picolyls) the tetrahydropyrimidine bromides of 1,3- bis- and 1.5 moles is stirred at room temperature 5 in ethanol Hour after, be spin-dried for solvent, residue is recrystallized with dichloromethane-ether, obtain tetrahydropyrimidine hexafluorophosphate sterling (1.75g, Yield 85%).
1,3- bis- (2- picolyls) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.82g) is added in Schlenk bottles And PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and pyridine (6mL), 140 DEG C of oil bath is stirred Mix 12h.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate is through column chromatographic isolation and purification (gradient elution, expansion Agent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (I).Colorless solid (0.64g, 58%)1H NMR(400MHz,DMSO-d6):δ9.00-8.98(m,2H,Py-H),8.22-8.18(m,2H,Py- ), H 7.88 (d, J=7.1Hz, 2H, Py-H), 7.67-7.63 (m, 2H, Py-H), 5.30 (d, J=15.1Hz, 2H, picolyl- CH2), 4.80 (d, J=15.3Hz, 2H, picolyl-CH2),3.58-3.48(m,4H,pyrimidine-CH2),1.92(t,J =5.8Hz, 2H, pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ174.9,154.8,154.0, 141.4,125.6,125.2,61.6,47.5,20.8ppm.Anal Cacld for C16H18ClF6N4PPd(551.99):C, 34.74；H,3.28；N,10.13.Found:C,34.56；H,3.02；N,9.89.
Embodiment 2
Pyridine-2-formaldehyde (30mmol, 3.21g) and 2,2- dimethyl -1,3- propane diamine (15mmol, 1.53g) are existed Mixed in 30mL methanol, after reacting at room temperature 7.0 hours, NaBH is slowly added under ice-water bath stirring4(120mmol, 4.54g), slowly Slowly 70 DEG C are warming up to react 5 hours.Stop reaction, be cooled to room temperature, be spin-dried for reaction solution.50mL CH are used again2Cl2Dissolving, filtering, Filtrate is spin-dried for, and obtains yellow oily dope.Above-mentioned yellow oily dope is dissolved in after 30mL methanol, then addition etc. rubs thereto You measure formalin, are stirred at room temperature after 3 hours, removal of solvent under reduced pressure, column chromatographic isolation and purification obtains 3,3- dimethyl -1,3- bis- (2- picolyls) hexahydropyrimidine (3.96g, yield 89%).
(2- picolyls) hexahydropyrimidine of 3,3- dimethyl -1,3- bis- (5mmol, 1.48g) is dissolved in 30mLDME, then to NBS (5mmol, 0.89g) is wherein added, is stirred at room temperature after 3 hours, suction filtration obtains pale yellow powder, is tied again through dichloromethane-ether It is brilliant to obtain 3,3- dimethyl -1,3- two (2- picolyls) tetrahydropyrimidine bromide.By (the 2- pyridine first of 3,3- dimethyl -1,3- two Base) tetrahydropyrimidine bromide and 1.5 moles ammonium hexafluorophosphate 5 hours are stirred at room temperature in ethanol after be evaporated, then use CH2Cl2 Dissolving, filtering, filtrate are rotated, residue recrystallizes to obtain (the 2- pyridine first of 3,3- dimethyl -1,3- bis- with dichloromethane-ether Base) tetrahydropyrimidine hexafluorophosphate sterling (1.89g, yield 86%).
(2- picolyls) the tetrahydropyrimidine hexafluorophosphates of 3,3- dimethyl -1,3- two are added in Schlenk bottles (2mmol, 0.88g) and PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and pyridine (6mL), 140 DEG C of stirring 12h of oil bath.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate is pure through column chromatography for separation Change (gradient elution, solvent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (II).Faint yellow solid (0.70g, 60%)1H NMR(400MHz,DMSO-d6):δ 9.01 (d, J=4.9Hz, 2H, Py-H), 8.23-8.19 (m, 2H, Py-H), 7.86 (d, J=7.4Hz, 2H, Py-H), 7.68-7.65 (m, 2H, Py-H), 5.38 (d, J= 15.1Hz,2H,picolyl-CH2), 4.77 (d, J=15.2Hz, 2H, picolyl-CH2), 3.28 (d, J=3.2Hz, 4H, pyrimidine-CH2),0.79(s,6H,CH3)ppm；13C NMR(100MHz,DMSO-d6):δ174.0,154.9,154.0, 141.5,125.5,125.2,61.6,58.7,28.1,23.5ppm；Anal Cacld forC18H22ClF6N4PPd(580.02): C,37.20；H,3.82；N,9.64；Found:C,36.93；H,3.87；N,9.49.
Embodiment 3
By 5- bromopyridine -2- formaldehyde (30mmol, 5.58g) and 1,3- propane diamine (15mmol, 1.11g) in 30mL methanol Mixing, after reacting at room temperature 5.0 hours, NaBH is slowly added under ice-water bath stirring4(120mmol, 4.54g), is slowly ramped to 70 DEG C reaction 5 hours.Stop reaction, be cooled to room temperature, be spin-dried for reaction solution.50mL CH are used again2Cl2Dissolving, filtering, filtrate are spin-dried for, Obtain yellow oily dope.Above-mentioned yellow oily dope is dissolved in after 30mL methanol, then adds equimolar amounts formaldehyde thereto The aqueous solution, is stirred at room temperature after 3 hours, removal of solvent under reduced pressure, and column chromatographic isolation and purification obtains 1,3- bis- (5- bromo-2-pyridyls methyl) six Hydrogen pyrimidine (5.30g, yield 83%).
1,3- bis- (5- bromo-2-pyridyls methyl) hexahydropyrimidine (5mmol, 2.13g) is dissolved in 30mL DME, then added thereto Enter NBS (5mmol, 0.89g), be stirred at room temperature after 3 hours, suction filtration obtains pale yellow powder, through dichloromethane-ether recrystallize 1, 3- bis- (5- bromo-2-pyridyls methyl) tetrahydropyrimidine bromide.By (5- bromine 2- picolyls) the tetrahydropyrimidine bromides of 1,3- bis- and The ammonium hexafluorophosphate of 1.5 moles is evaporated after 5 hours are stirred at room temperature in ethanol, then uses CH2Cl2Dissolving, filtering, filtrate is revolved Steam, residue recrystallized with dichloromethane-ether 1,3- bis- (5- bromine 2- picolyls) tetrahydropyrimidine hexafluorophosphate is pure Product (2.42g, yield 85%).
Added in Schlenk bottles 1,3- bis- (5- bromo-2-pyridyls methyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 1.14g) and PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and pyridine (6mL), oil bath 140 DEG C of stirring 12h.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate through column chromatographic isolation and purification (wash by gradient It is de-, solvent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (III).It is pale yellow Color solid (0.75g, 53%)1H NMR(400MHz,DMSO-d6):δ9.10-9.08(s,2H,Py-H),8.32-8.28(d,J =7.1Hz, 2H, Py-H), 7.98 (d, J=7.1Hz, 2H, Py-H), 5.35 (d, J=15.1Hz, 2H, picolyl-CH2), 4.86 (d, J=15.2Hz, 2H, picolyl-CH2),3.63-3.54(m,4H,pyrimidine-CH2), 1.97 (t, J= 5.8Hz,2H,pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ174.8,154.3,153.6,141.0, 125.1,124.7,61.5,47.3,20.6ppm.Anal Cacld for C16H16Br2ClF6N4PPd(707.81):C, 27.03；H,2.27；N,7.88.Found:C,27.28；H,2.09；N,7.70.
Embodiment 4
By 5- bromopyridine -2- formaldehyde (30mmol, 5.58g) and 2,2- dimethyl -1,3- propane diamine (15mmol, 1.53g) Mixed in 30mL methanol, after reacting at room temperature 7.0 hours, NaBH is slowly added under ice-water bath stirring4(120mmol, 4.54g), 70 DEG C are slowly ramped to react 5 hours.Stop reaction, be cooled to room temperature, be spin-dried for reaction solution.50mL CH are used again2Cl2Dissolving, mistake Filter, filtrate is spin-dried for, and obtains yellow oily dope.Above-mentioned yellow oily dope is dissolved in after 30mL methanol, then added thereto Equimolar amounts formalin, is stirred at room temperature after 3 hours, removal of solvent under reduced pressure, and column chromatographic isolation and purification obtains 3,3- dimethyl -1, 3- bis- (5- bromo-2-pyridyls methyl) hexahydropyrimidine (5.52g, yield 81%).
3,3- dimethyl -1,3- two (5- bromo-2-pyridyls methyl) hexahydropyrimidine (5mmol, 2.27g) is dissolved in 30mL DME, then NBS (5mmol, 0.89g) is added thereto, it is stirred at room temperature after 3 hours, suction filtration obtains pale yellow powder, through dichloromethane- Diethyl ether recrystallization obtains 3,3- dimethyl -1,3- two (5- bromo-2-pyridyls methyl) tetrahydropyrimidine bromide.By 3,3- dimethyl -1, It is small that the ammonium hexafluorophosphate of (5- bromo-2-pyridyls methyl) the tetrahydropyrimidine bromides of 3- bis- and 1.5 moles is stirred at room temperature 5 in ethanol When after be evaporated, then use CH2Cl2Dissolving, filtering, filtrate are rotated, residue recrystallizes to obtain 3,3- diformazans with dichloromethane-ether Base -1,3- bis- (5- bromo-2-pyridyls methyl) tetrahydropyrimidine hexafluorophosphate sterling (2.51g, yield 84%).
(5- bromo-2-pyridyls methyl) the tetrahydropyrimidine hexafluorophosphoric acids of 3,3- dimethyl -1,3- two are added in Schlenk bottles Salt (2mmol, 1.20g) and PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and pyridine (6mL), 140 DEG C of stirring 12h of oil bath.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate is pure through column chromatography for separation Change (gradient elution, solvent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (IV).Light yellow solid (0.81g, 55%)1H NMR(400MHz,DMSO-d6):δ9.11(s,2H,Py-H),8.32-8.29 (d, J=7.5Hz, 2H, Py-H), 7.96 (d, J=7.5Hz, 2H, Py-H), 5.43 (d, J=15.2Hz, 2H, picolyl- CH2), 4.82 (d, J=15.2Hz, 2H, picolyl-CH2), 3.32 (d, J=3.2Hz, 4H, pyrimidine-CH2),0.84 (s,6H,CH3)ppm；13C NMR(100MHz,DMSO-d6):δ174.1,154.4,153.5,141.0,125.1,124.7, 61.4,58.5,27.9,23.3ppm；Anal Cacld for C18H20Br2ClF6N4PPd(735.84):C,29.25；H, 2.73；N,7.58；Found:C,29.10；H,2.87；N,7.40.
Embodiment 5
By 6- bromopyridine -2- formaldehyde (30mmol, 5.58g) and 1,3- propane diamine (15mmol, 1.11g) in 30mL methanol Mixing, after reacting at room temperature 5.0 hours, NaBH is slowly added under ice-water bath stirring4(120mmol, 4.54g), is slowly ramped to 70 DEG C reaction 5 hours.Stop reaction, be cooled to room temperature, be spin-dried for reaction solution.50mL CH are used again2Cl2Dissolving, filtering, filtrate are spin-dried for, Obtain yellow oily dope.Above-mentioned yellow oily dope is dissolved in after 30mL methanol, then adds equimolar amounts formaldehyde thereto The aqueous solution, is stirred at room temperature after 3 hours, removal of solvent under reduced pressure, and column chromatographic isolation and purification obtains 1,3- bis- (6- bromo-2-pyridyls methyl) six Hydrogen pyrimidine (5.25g, yield 82%).
1,3- bis- (6- bromo-2-pyridyls methyl) hexahydropyrimidine (5mmol, 2.13g) is dissolved in 30mL DME, then added thereto Enter NBS (5mmol, 0.89g), be stirred at room temperature after 3 hours, suction filtration obtains pale yellow powder, through dichloromethane-ether recrystallize 1, 3- bis- (6- bromo-2-pyridyls methyl) tetrahydropyrimidine bromide.By (6- bromine 2- picolyls) the tetrahydropyrimidine bromides of 1,3- bis- and The ammonium hexafluorophosphate of 1.5 moles is evaporated after 5 hours are stirred at room temperature in ethanol, then uses CH2Cl2Dissolving, filtering, filtrate is revolved Steam, residue recrystallized with dichloromethane-ether 1,3- bis- (6- bromine 2- picolyls) tetrahydropyrimidine hexafluorophosphate is pure Product (2.36g, yield 83%).
Added in Schlenk bottles 1,3- bis- (6- bromo-2-pyridyls methyl) tetrahydropyrimidine hexafluorophosphate (2mmol, 1.14g) and PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and pyridine (6mL), oil bath 140 DEG C of stirring 12h.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate through column chromatographic isolation and purification (wash by gradient It is de-, solvent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (V).It is light yellow Solid (0.78g, 55%)1H NMR(400MHz,DMSO-d6):δ 8.27-8.23 (m, 2H, Py-H), 7.93 (d, J=7.2Hz, 2H, Py-H), 7.72-7.68 (m, 2H, Py-H), 5.33 (d, J=15.2Hz, 2H, picolyl-CH2), 4.83 (d, J= 15.3Hz,2H,picolyl-CH2),3.62-3.53(m,4H,pyrimidine-CH2), 1.95 (t, J=5.8Hz, 2H, pyrimidine-CH2)ppm.13C NMR(100MHz,DMSO-d6):δ175.0,155.3,154.4,141.9,126.0, 125.6,61.9,47.8,21.0ppm.Anal Cacld for C16H16Br2ClF6N4PPd(707.81):C,27.03；H, 2.27；N,7.88.Found:C,27.30；H,2.08；N,7.65.
Embodiment 6
By 6- bromopyridine -2- formaldehyde (30mmol, 5.58g) and 2,2- dimethyl -1,3- propane diamine (15mmol, 1.53g) Mixed in 30mL methanol, after reacting at room temperature 7.0 hours, NaBH is slowly added under ice-water bath stirring4(120mmol, 4.54g), 70 DEG C are slowly ramped to react 5 hours.Stop reaction, be cooled to room temperature, be spin-dried for reaction solution.50mL CH are used again2Cl2Dissolving, mistake Filter, filtrate is spin-dried for, and obtains yellow oily dope.Above-mentioned yellow oily dope is dissolved in after 30mL methanol, then added thereto Equimolar amounts formalin, is stirred at room temperature after 3 hours, removal of solvent under reduced pressure, and column chromatographic isolation and purification obtains 3,3- dimethyl -1, 3- bis- (6- bromo-2-pyridyls methyl) hexahydropyrimidine (5.23g, yield 77%).
3,3- dimethyl -1,3- two (6- bromo-2-pyridyls methyl) hexahydropyrimidine (5mmol, 2.27g) is dissolved in 30mL DME, then NBS (5mmol, 0.89g) is added thereto, it is stirred at room temperature after 3 hours, suction filtration obtains pale yellow powder, through dichloromethane- Diethyl ether recrystallization obtains 3,3- dimethyl -1,3- two (6- bromo-2-pyridyls methyl) tetrahydropyrimidine bromide.By 3,3- dimethyl -1, It is small that the ammonium hexafluorophosphate of (6- bromo-2-pyridyls methyl) the tetrahydropyrimidine bromides of 3- bis- and 1.5 moles is stirred at room temperature 5 in ethanol When after be evaporated, then use CH2Cl2Dissolving, filtering, filtrate are rotated, residue recrystallizes to obtain 3,3- diformazans with dichloromethane-ether Base -1,3- bis- (6- bromo-2-pyridyls methyl) tetrahydropyrimidine hexafluorophosphate sterling (2.60g, yield 87%).
(6- bromo-2-pyridyls methyl) the tetrahydropyrimidine hexafluorophosphoric acids of 3,3- dimethyl -1,3- two are added in Schlenk bottles Salt (2mmol, 1.20g) and PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and pyridine (6mL), 140 DEG C of stirring 12h of oil bath.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate is pure through column chromatography for separation Change (gradient elution, solvent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (VI).Light yellow solid (0.75g, 51%)1H NMR(400MHz,DMSO-d6):δ8.28-8.24(m,2H,Py-H),7.90 (d, J=7.3Hz, 2H, Py-H), 7.73-7.70 (m, 2H, Py-H), 5.40 (d, J=15.1Hz, 2H, picolyl-CH2), 4.81 (d, J=15.2Hz, 2H, picolyl-CH2), 3.30 (d, J=3.1Hz, 4H, pyrimidine-CH2),0.80(s,6H, CH3)ppm；13C NMR(100MHz,DMSO-d6):δ174.1,155.4,154.5,141.9,125.9,125.7,62.0, 59.0,28.3,23.8ppm；Anal Cacld for C18H20Br2ClF6N4PPd(735.84):C,29.25；H,2.73；N, 7.58；Found:C,28.99；H,2.80；N,7.43.
Embodiment 7
Other steps are ibid.
1,3- bis- (2- picolyls) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.82g) is added in Schlenk bottles And PdCl2(2mmol, 0.35g), argon gas protection is lower to add NaN (SiMe3)2(2.1mmol) and toluene (8mL), 120 DEG C of oil bath is stirred Mix 20h.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate is through column chromatographic isolation and purification (gradient elution, expansion Agent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (I).Data are shown in that implementation is real Example 1.
Embodiment 8：
Other steps are ibid.
1,3- bis- (2- picolyls) tetrahydropyrimidine hexafluorophosphate (2mmol, 0.82g) is added in Schlenk bottles And PdCl2(2mmol, 0.35g), argon gas protection is lower to add KN (SiMe3)2(2.1mmol) and pyridine (6mL), 140 DEG C of oil bath is stirred Mix 12h.After reaction terminates, reaction solution is cooled to room temperature, filtered, filtrate is through column chromatographic isolation and purification (gradient elution, expansion Agent：N-hexane/dichloromethane=1/10~1/20), obtain pincerlike ring expansion N-heterocyclic carbine palladium compound (I).Data are shown in embodiment 1。
Application examples：
Part C-N coupled catalytic reaction examples：
By halogenated aryl hydrocarbon (1.0mmol), amine (3.0mmol), alkali (2.0mmol), the pincerlike ring expansion N-heterocyclic carbine of the present invention Palladium compound catalyst (0.01mmol) is added in solvent, under microwave radiation after 50~100 DEG C are reacted 10~40 minutes, drop To room temperature, removal of solvent under reduced pressure, pillar layer separation obtains sterling.
Partially catalyzed reaction result such as following table：
It is fine that data above shows that synthesized pincerlike ring expansion N-heterocyclic carbine palladium compound has to C-N coupling reactions Catalytic effect.And C-N coupling reactions have important ground in organic synthesis, medicament research and development and functional material exploitation etc. Position, the pincerlike ring expansion N-heterocyclic carbine palladium compound that the present invention is synthesized has good application prospect.

Claims (1)

1. the following ring expansion N-heterocyclic carbine palladium compound containing picolyl of structural formula answering in catalysis C-N coupling reactions With, it is characterised in that it is achieved by the steps of：
,
Ring expansion N-heterocyclic carbine palladium compound catalyst, alkali, halogenated aryl hydrocarbon, amine containing picolyl are added in solvent, Under microwave radiation after 50 ~ 100 DEG C are reacted 10 ~ 40 minutes, room temperature is down to, removal of solvent under reduced pressure, pillar layer separation obtains arylamine.
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