CN102816183A - Synthesis method of novel dinaphthalene skeleton-based n-heterocyclic carbenes-phosphine compounds and metal complex thereof - Google Patents
Synthesis method of novel dinaphthalene skeleton-based n-heterocyclic carbenes-phosphine compounds and metal complex thereof Download PDFInfo
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- 0 Nc1ccc(cccc2)c2c1-c1c(cccc2)c2cc*1P(c1ccccc1)(c1ccccc1)=S Chemical compound Nc1ccc(cccc2)c2c1-c1c(cccc2)c2cc*1P(c1ccccc1)(c1ccccc1)=S 0.000 description 3
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Abstract
The invention relates to a synthesis method of novel chiral dinaphthalene skeleton-based n-heterocyclic carbenes-phosphine compounds and metal complex thereof. The carbene and phosphine ligands are the important ligands in the field of homogeneous catalysis, but the two ligands are hardly connected with each other by a certain skeleton since the trivalent phosphine can be formed into the salt with the halohydrocarbon to loss the ligancy mainly. By virtue of the design of a synthetic route, the sulphur is ingeniously used, so that the phosphine is easy to oxidize, the protection is carried out, and the defects in the prior art can be smoothly solved due to the characteristic of raney nickel removal, a dinaphthalene skeleton-based n-heterocyclic carbenes-phosphine compound precursor can be smoothly synthesized, and the carbene-phosphine ligand can be obtained by the carbene precursor imidazolium salt under the effect of alkali, so that the ligand metal complexes has completely different expression on the reactivity compared with the mono-carbene metal complex or the mono-phosphine metal complex, and can be widely used for preparing the catalyst for the asymmetric catalytic reaction. The chiral dinaphthalene skeleton-based n-heterocyclic carbenes-phosphine compound and the metal complex thereof provided by the invention have the structural formulae shown in the specification, wherein R can be various substituent groups or functional groups.
Description
Technical field
The present invention relates to a kind of novel based on dinaphthalene skeleton N-heterocyclic carbine phosphine compound and metal complex synthetic novel method thereof.
Background technology
N-heterocyclic carbine has the character that strong σ gives body and weak π acceptor, make this type part can not only with all transition metal with low or high valence state complexing, and can with the complexing of part main group element.Thereby make N-heterocyclic carbine in Organometallic Chemistry, obtain using widely as part.And classical phosphine part has the coordination stable in properties, the active high plurality of advantages of metal complex, and therefore how through a specific skeleton two kinds of outstanding parts being coupled together the fellowship coordination becomes the focus and the difficult point of Organometallic Chemistry research.
Group of different nature and the common coordination of N-heterocyclic carbine are referred to as the functionalization Cabbeen.Lin ， oxazoline in the past 20 years, pyridines, the Cabbeen of imines class functionalization all is seen in report; Can find that through experimental result the Cabbeen of functionalization has demonstrated different character and catalytic activity, their metal complex can the catalysis series reaction, comprising: Heck, Suzuki; Kumada, Sonogashira, linked reactions such as Stille, olefin metathesis; Hydrosilation, aromatic hydrocarbons amination, hydrocarbon activation, hydro-reduction; Alkene is Cyclopropanated, the aryl of aldehyde and alkenyl, oxidation, reactions such as allyl group replacement.
Imidazoline salt can obtain corresponding carbene precursor under the effect of alkali, can generate corresponding metal carbene complex, these complex compound widespread use organic synthesis and asymmetric catalysis field thereof with various metal complexes or original position.
Literature search finds, synthetic based on the N-heterocyclic carbine phosphine compound of dinaphthalene skeleton do not arranged at present.
The invention provides a kind of compound method based on the N-heterocyclic carbine phosphine compound and the metal complex thereof of dinaphthalene skeleton, reaction conditions is gentle, and step is simple.Route is reasonable, no poisonous and harmful reagent.Therefore, the present invention is a kind of energy-efficient, green compound method.
Summary of the invention
The present invention relates to a kind of N-heterocyclic carbine phosphine compound and metal complex synthetic novel method thereof based on the dinaphthalene skeleton.Its compound method is: with the dinaphthalene ethanamide triflate A of chirality in palladium; Diaryl or alkylphosphines oxygen; Dppb; Under the existence of diisopropyl ethyl amine, be the dinaphthalene ethanamide phosphine oxide compound B that solvent reaction obtains chirality with DMSO, dinaphthalene ethanamide phosphine oxide compound B deacetylate under the effect of hydrochloric acid soln obtains the amino phosphine oxide compound C of dinaphthalene.Dinaphthalene phosphine oxide compound C carries out hydrosilation reaction through trichlorosilane and obtains the amino phosphine compound D of dinaphthalene.Amino phosphine compound D of dinaphthalene and the reaction of sulphur powder obtain the amino phosphine sulfide compd E of dinaphthalene.The amino phosphine sulfide compd E of dinaphthalene is at oxalic dialdehyde, the effect of Paraformaldehyde 96 and ammonium chloride next step close ring arrive dinaphthalene imidazoles phosphine sulfide compound F 17-hydroxy-corticosterone.Dinaphthalene imidazoles phosphine sulfide compound F 17-hydroxy-corticosterone obtains dinaphthalene phosphine sulfide imidazole salts compound G at the effect salify of halohydrocarbon.Compound G sloughs sulphur under the effect of Raney's nickel can obtain dinaphthalene phosphine imidazole salts compound H.Dinaphthalene ethanamide triflate A can be under the catalysis of palladium through pressure hydration to H8-dinaphthalene compound I.Compd A or I can obtain 3 under the effect of bromine, the dinaphthalene compound J of 3 '-bromo, compound J can the suzuki coupling take place with different types of boronic acid compounds and obtain corresponding dinaphthalene compound K.
This compound method is simple, and the imidazoline salt that obtains can obtain Cabbeen-phosphine part under the effect of alkali, and this type part can be widely used in asymmetric catalysis.
N-heterocyclic carbine phosphine compound and metal complex thereof based on the dinaphthalene skeleton provided by the invention, its structural formula is following:
R wherein
1, R
2, R
4And R
5Can be alkyl and the various chirality alkyl or the chiral aryl of hydrogen phenyl, naphthyl, various aryl and substituted aryl, heterocyclic aryl (thiophene, pyrroles etc.), 1-8 carbon; R
3And R
6Can be alkyl, C2～C8 naphthenic base, C2～C6 thiazolinyl, various replacement propargyl, benzyl and various substituted benzyl, the substituted methylene radical of aromatic hydrocarbon of C1～C6 straight or branched; R
7And R
8Can be alkyl, C5～C8 naphthenic base, aryl, aralkyl, the single replacement and polysubstituted aryl, heterocyclic aryl etc. of C1～C6 straight or branched; X can be halogen, tetrafluoroborate, hexafluoroantimonic anion, hexafluoro-phosphate radical, BArF
-, tetraphenyl borate, carboxylate radical, fluorocarboxylic acid root, trifluoromethanesulfonic acid root, cyanic acid negative ion etc.M is a kind of among various transition metal Ru, Rh, Pd, Ir, Pt, Cu, Ag, the Au.
Embodiment
A kind of prepare of the present invention based on the N-heterocyclic carbine phosphine compound of dinaphthalene skeleton and the method for metal complex thereof.Reaction formula is following:
Concrete synthesis step is following: in the three-necked flask that had toasted, add compd A, disubstituted phosphine oxygen, palladium, dppb; Substitute argon gas, add DMSO and diisopropyl ethyl amine, be warming up to 100 ℃, reaction TLC detects and disappears up to raw material; Unnecessary solvent is removed in distillation, EA diluted system, washing; Anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains compd B.
Compd B is inserted round-bottomed flask, add dissolve with ethanol, add the 4M hydrochloric acid soln again, be warming up to backflow; TLC detects up to raw material and disappears, saturated sodium bicarbonate solution cancellation reaction, dichloromethane extraction; Anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains Compound C.
In the there-necked flask that had toasted, add Compound C, substitute argon gas three times, add toluene and triethylamine, be cooled to 0 ℃; Add trichlorosilane, reaction rises to backflow, and TLC detects and disappears up to raw material; Saturated sodium carbonate solution cancellation reaction, the zeyssatite suction filtration is removed insoluble solids, dichloromethane extraction; Anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains Compound D.
Add the sulphur powder in the there-necked flask that toasted, Compound D is dissolved in and adds reaction system in the methylene dichloride.Stop behind the reaction 12h, directly revolve the dry system rapid column chromatography and obtain compd E.
Compd E is added in the flask, add deionized water and a SPA, stir and add glyoxal water solution after 5 minutes, Paraformaldehyde 96 and 1; The 4-dioxane is warming up to 75 ℃ gradually, adds ammonium chloride, reacts to be warming up to 100 ℃ after 5 minutes; TLC detects up to raw material and disappears, saturated sodium carbonate solution cancellation reaction, dichloromethane extraction; Anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains compound F 17-hydroxy-corticosterone.
Compound F 17-hydroxy-corticosterone is inserted in the flask, add the acetonitrile dissolving, add halohydrocarbon again, reaction is warming up to backflow, and TLC detects up to raw material and disappears, the dried solvent of decompression underspin, and the yellow solid G that obtains can directly apply to next step reaction and need not to handle.
Toasted in the reaction tubes of argon shield and add Raney's nickel, compound G is dissolved in and adds reaction system in the acetonitrile, and reaction is 1 day under the room temperature, after reaction finishes, and zeyssatite elimination nickel, the dried solvent of decompression underspin obtains compound H.
Compd A adds in the autoclave, adds palladium charcoal and solvent, and pressurized with hydrogen is to 50atm, and 100 ℃ are reacted 24h down, after reaction finishes, and the elimination catalyzer, the dried solvent of decompression underspin, the crude product rapid column chromatography obtains the H8-compound I.
Compd A is dissolved in the THF, slowly adds NBS, dropwises the back room temperature reaction.TLC detects up to raw material and disappears, saturated sodium carbonate solution cancellation reaction, and dichloromethane extraction, anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains compound J.
In the reaction tubes that toasted, add compound J, palladium and potassium tert.-butoxide add 1, and the dissolving of 4-dioxane is warming up to 80 ℃, and TLC detects up to raw material and disappears, and system is directly revolved dried rapid column chromatography, obtains compound K.
In the eggplant-shape bottle that has toasted, add compound H-1 or H-2 and metallic compound; Adding THF then; The dissolving back adds potassium tert.-butoxide, stirs after 10 minutes, is heated to 60 ℃ and stirs 24 hours; Directly revolve driedly after reaction finishes, thick product separates with rapid column chromatography and obtains chiral binaphthyl N-heterocyclic carbine phosphine metal complex L-1 or L-2.
Institute of the present invention synthetic chiral binaphthyl N-heterocyclic carbine phosphine compound and metal complex thereof typically comprise the compound of following structural, but are not limited thereto.
Through embodiment this outbreak is further set forth below, its purpose only is better to understand content of the present invention.The example of therefore, being lifted does not limit protection scope of the present invention.
Embodiment 1
(1) preparation dinaphthalene ethanamide phosphine oxide compound B
In the three-necked flask that had toasted, add compd A (3.2g, 7mmol), diphenylphosphine oxygen (2.83g, 14mmol), palladium (154mg; 0.7mmol), (300mg 0.7mmol), substitutes argon gas to dppb, adds DMSO (50ml) and diisopropyl ethyl amine (4.8ml; 28mmol), be warming up to 100 ℃, reaction TLC detects up to raw material and disappears, and unnecessary solvent, EA diluted system are removed in distillation; Washing, anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains the 1.9g compd B.
1H?NMR(400MHz，CDCl
3)：δ9.74(s，1H)，7.97-7.89(m，4H)，7.71-7.70(m，2H)，7.64-7.52(m，6H)，7.25-7.11(m，5H)，6.98-6.55(m，5H)，1.92(s，1H).
31P?NMR(75Hz，CDCl
3)：δ29.53.
(2) the amino phosphine oxide compound C of preparation dinaphthalene
(1.9g 4mmol) inserts round-bottomed flask, adds ethanol (30ml) dissolving with compd B; Add 4M hydrochloric acid soln (30ml) again, be warming up to backflow, TLC detects and disappears up to raw material; Saturated sodium bicarbonate solution cancellation reaction, dichloromethane extraction, anhydrous sodium sulfate drying; The decompression underspin desolvates, and rapid column chromatography obtains the 1.75g Compound C.
1H?NMR(400MHz，CDCl
3)：δ7.97-7.92(m，2H)，7.90-7.69(m，3H)，7.55(t，J＝6.8Hz，1H)，7.46-7.39(m，5H)，7.29-7.22(m，5H)，7.02(t，J＝6.8Hz，1H)，6.96-6.77(m，5H)，6.51(d，J＝8.4Hz，1H)，3.89(br，2H).
31P?NMR(75Hz，CDCl
3)：δ28.73.
(3) the amino phosphine compound D of preparation dinaphthalene
(1.74g 3.7mmol), substitutes argon gas three times, adds toluene (60ml) and triethylamine (5ml in the there-necked flask that had toasted, to add Compound C; 29.6mmol), be cooled to 0 ℃, and the adding trichlorosilane (1.5ml, 14.8mmol); Reaction rises to backflow, and TLC detects up to raw material and disappears, saturated sodium carbonate solution cancellation reaction, and the zeyssatite suction filtration is removed insoluble solids; Dichloromethane extraction, anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains the 0.99g Compound D.
1H?NMR(400MHz，CDCl
3)：δ7.97-7.92(m，2H)，7.90-7.69(m，3H)，7.62(t，J＝10.6Hz，1H)，7.46-7.39(m，5H)，7.29-7.22(m，5H)，7.02(t，J＝10.6Hz，1H)，6.96-6.77(m，6H)，3.72(br，2H).
31PNMR(75Hz，CDCl
3)：δ-15.46
(4) the amino phosphine sulfide compd E of preparation dinaphthalene
(160mg, 5mmol), (450mg 1mmol) is dissolved in and adds reaction system in the methylene dichloride Compound D in the there-necked flask that toasted, to add the sulphur powder.Stop behind the reaction 12h, directly revolve the dry system rapid column chromatography and obtain the 478mg compd E.
1H?NMR(400MHz，CDCl
3)：δ7.96-7.79(m，5H)，7.52(t，J＝7.6Hz，1H)，7.41-7.33(m，7H)，7.24(t，J＝7.6Hz，1H)，7.13-7.02(m，3H)，6.86-6.65(m，5H)，3.78(br，2H).
31P?NMR(75Hz，CDCl
3)：δ43.31
(5) preparation dinaphthalene imidazoles phosphine sulfide compound F 17-hydroxy-corticosterone
In the 100mL round-bottomed flask, add compd E (485mg, 1.0mmol), deionized water 10mL, glyoxal water solution (2.5mmol), Paraformaldehyde 96 (75mg); 1 SPA and 1,4-dioxane 10mL is warming up to 70 ℃; Add ammonium chloride (134mg; 2.5mmol), 70 ℃ were stirred 10 minutes down, rise to 100 ℃ of reactions again and disappear up to raw material.Add the saturated sodium carbonate solution cancellation, revolve driedly behind dichloromethane extraction, the anhydrous magnesium sulfate drying, thick product separates with rapid column chromatography and obtains dinaphthalene imidazoles phosphine sulfide compound F 17-hydroxy-corticosterone 349mg.
1H?NMR(400MHz，CDCl
3)：δ7.91-7.82(m，4H)，7.63-7.54(m，2H)7.42-7.04(m，15H)，7.41-7.33(m，7H)，7.04(t，J＝6.0Hz，1H)，6.81(d，J＝8.4Hz，1H)，6.84(s，13H)，6.76(s，1H).
31PNMR(75Hz，CDCl
3)：δ43.80.
(6) preparation dinaphthalene phosphine sulfide imidazole salts compound G
Compound F 17-hydroxy-corticosterone is inserted in the flask, add the acetonitrile dissolving, add halohydrocarbon again, reaction is warming up to backflow, and TLC detects up to raw material and disappears, the dried solvent of decompression underspin, and the yellow solid G that obtains can directly apply to next step reaction and need not to handle.
1H?NMR(400MHz，CDCl
3)：δ10.05(s，1H)，8.17(d，J＝8.8Hz，1H)，8.00-7.43(m，14H)，7.24-6.76(m，9H)，6.47(s，2H)，4.09(s，3H).
31P?NMR(75Hz，CDCl
3)：δ42.47.
(7) preparation dinaphthalene phosphine imidazole salts compound H
Toasted in the reaction tubes of argon shield and added Raney's nickel (500mg), and compound G (68mg 0.1mmol) is dissolved in and adds reaction system in the acetonitrile, and reaction is 1 day under the room temperature, after reaction finishes, and zeyssatite elimination nickel, the dried solvent of decompression underspin obtains the 60mg compound H.
1H?NMR(400MHz，CDCl
3)：δ8.83(s，1H)，8.27-8.21(m，2H)，8.02-7.92(m，3H)，7.61-7.30(m，7H)，7.24-6.51(m，12H)，6.50(s，1H)，3.77(s，3H).
31P?NMR(75Hz，CDCl
3)：δ-15.13.
Embodiment 2
Except the initial feed preparation, other step is identical with embodiment 1, can make chiral binaphthyl N-heterocyclic carbine-phosphine compound C-3
(1) the triflated compound I of preparation H8-dinaphthalene ethanamide
Compd A (3.2g 7mmol) adds in the autoclave, adds palladium charcoal (1g) and solvent, and pressurized with hydrogen is to 50atm, and 100 ℃ are reacted 24h down, after reaction finishes, and the elimination catalyzer, the dried solvent of decompression underspin, the crude product rapid column chromatography obtains the 4gH8-compound I.
1H?NMR(400MHz，CDCl
3)：δ8.25(s，1H)，7.79-7.76(m，4H)，3.25，-2.75(m，8H)，2.15(s，3H)，1.82-1.55(m，8H).
Embodiment 3
Except the initial feed preparation, other step is identical with embodiment 1,2, and the method for other aryl and alkylboronic acids is identical with (2), all can make 3,3 '-substituted chiral binaphthyl N-heterocyclic carbine-phosphine compound C-1 and C-3
(1) preparation 3, the triflated compound J of the dinaphthalene ethanamide of 3 '-bromo
(3.2g 7mmol) is dissolved in the THF compd A, and (2.5g 10mmol), dropwises the back room temperature reaction slowly to add NBS.TLC detects up to raw material and disappears, saturated sodium carbonate solution cancellation reaction, and dichloromethane extraction, anhydrous sodium sulfate drying, the decompression underspin desolvates, and rapid column chromatography obtains 3.8g compound J.
1H?NMR(400MHz，CDCl
3)：δ9.74(s，1H)，7.97-7.89(m，4H)，7.71-7.70(m，2H)，7.64-7.52(m，4H)，1.92(s，1H).
(2) preparation 3, the triflated compound K of the dinaphthalene ethanamide of 3 '-phenyl
Adding compound J in the 25mL eggplant-shape bottle that has toasted (62mg, 0.1mmol), phenyl-boron dihydroxide (45mg; 0.25mmol),, acid chloride (0.005mmol); Sodium methylate (12mg, 0.22mmol), 1; 4-dioxane 10mL heats under the argon shield condition, and the TLC plate is followed the tracks of, and J reacts completely until compound.Revolve dried solvent, rapid column chromatography obtains 70mg3, the triflated compound K of the dinaphthalene ethanamide of 3 '-phenyl.
1H?NMR(400MHz，CDCl
3)：δ9.74(s，1H)，7.97-7.89(m，4H)，7.71-7.70(m，2H)，7.64-7.52(m，4H)，7.25-7.11(m，5H)，6.98-6.55(m，5H)，1.92(s，1H).
Embodiment 4
According to instance 1,2, identical complex compound method shown in the equal use-case 4 of all kinds chiral binaphthyl skeleton imidazoles phosphonium salt of 3 preparations, this method is applicable to palladium, rhodium, iridium, silver, the preparation of transition metal such as copper.
(1) preparation dinaphthalene skeleton N-heterocyclic carbine phosphine palladium complex L-1
In the reaction tubes of the 25mL that has toasted, add respectively imidazole salts H-1 (65mg, 0.1mmol), palladium (0.1mmol; 23mg), and potassiumiodide (0.2mmol, 30mg); Substitute gas, under argon shield, add new steaming THF 5mL backflow and spend the night, raw material reaction finishes; The zeyssatite suction filtration, the decompression underspin desolvates, and thick product separates (SiO with rapid column chromatography
2, eluent is petrol ether/ethyl acetate=20/1) and obtain 75mg dinaphthalene skeleton N-heterocyclic carbine phosphine palladium complex L-1.
1H?NMR(400MHz，CDCl
3)：δ8.17(d，J＝8.8Hz，1H)，7.97(d，J＝8.8Hz，1H)，7.84(t，J＝8.08Hz，1H)，7.77-7.21(m，11H)，6.95(d，J＝8.4Hz，2H)，6.85-6.59(m，5H)，6.86(d，J＝8.8Hz，1H)，3.97(s，3H).
31P?NMR(75Hz，CDCl
3)：δ20.41.
Claims (5)
1. chirality N-heterocyclic carbine-phosphine compound provided by the invention and metal complex thereof, its structural formula is following:
Wherein, R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Independently be selected from respectively with X: the alkyl of hydrogen or C1～C6 straight or branched; C2～C8 naphthenic base, C2～C6 thiazolinyl, alkynyl, aryl, aralkyl or arylalkenyl, aryloxy, alkoxyl group, halogen, nitro, ester group, carboxamido-group, trifluoromethyl, cyanic acid or contain in the alkyl of C2～C6 thiazolinyl group, ethynylene group, aryl group, aralkyl group or arylalkenyl group, aryloxy group, alkoxy grp, halogen, nitro group, ester group, amide group, fluoroform group, cyanic acid group a kind of.
2. chirality N-heterocyclic carbine as claimed in claim 1-imidazoline salt compound and metal complex thereof is characterized in that: R
1, R
2, R
4And R
5Can be alkyl and the various chirality alkyl or the chiral aryl of hydrogen phenyl, naphthyl, various aryl and substituted aryl, heterocyclic aryl (thiophene, pyrroles etc.), 1-8 carbon; R
3And R
6Can be alkyl, C2～C8 naphthenic base, C2～C6 thiazolinyl, various replacement propargyl, benzyl and various substituted benzyl, the substituted methylene radical of aromatic hydrocarbon of C1～C6 straight or branched; R
7And R
8Can be alkyl, C5～C8 naphthenic base, aryl, aralkyl, the single replacement and polysubstituted aryl, heterocyclic aryl etc. of C1～C6 straight or branched; X can be halogen, tetrafluoroborate, hexafluoroantimonic anion, hexafluoro-phosphate radical, BArF
-, tetraphenyl borate, carboxylate radical, fluorocarboxylic acid root, trifluoromethanesulfonic acid root, cyanic acid negative ion etc.
3. the chirality N-heterocyclic carbine-phosphine compound and the metal complex thereof that require like right 1～2 is characterized in that, through designing a rational reaction scheme, make preparation condition simply gentle, and processing ease can acceptablely obtain new title product.
4. preparation is like the method for any described chirality chirality N-heterocyclic carbine-phosphine compound and metal complex thereof in the claim 1～4; It is characterized in that; Said preparation method is: with the dinaphthalene ethanamide triflate A of chirality in palladium; Diaryl or alkylphosphines oxygen, dppb is under the existence of diisopropyl ethyl amine; With DMSO is the dinaphthalene ethanamide phosphine oxide compound B that solvent reaction obtained chirality in 16 hours, and dinaphthalene ethanamide phosphine oxide compound B deacetylate under the effect of hydrochloric acid soln obtains the amino phosphine oxide compound C of dinaphthalene.Dinaphthalene phosphine oxide compound C carries out hydrosilation reaction through trichlorosilane and obtains the amino phosphine compound D of dinaphthalene.Amino phosphine compound D of dinaphthalene and the reaction of sulphur powder obtain the amino phosphine sulfide compd E of dinaphthalene.The amino phosphine sulfide compd E of dinaphthalene is at oxalic dialdehyde, the effect of Paraformaldehyde 96 and ammonium chloride next step close ring arrive dinaphthalene imidazoles phosphine sulfide compound F 17-hydroxy-corticosterone.Dinaphthalene imidazoles phosphine sulfide compound F 17-hydroxy-corticosterone obtains dinaphthalene phosphine sulfide imidazole salts compound G at the effect salify of halohydrocarbon.Compound G sloughs sulphur under the effect of Raney's nickel can obtain dinaphthalene phosphine imidazole salts compound H.Dinaphthalene ethanamide triflate A can be under the catalysis of palladium through pressure hydration to H8-dinaphthalene compound I.Compd A or I can obtain 3 under the effect of NBS, the dinaphthalene compound J of 3 '-bromo, compound J can the suzuki coupling take place with different types of boronic acid compounds and obtain corresponding dinaphthalene compound K.Its synthetic route is as follows
5. like the chiral binaphthyl N-heterocyclic carbine phosphine compound of right 4 requirements and the preparation method of metal complex thereof; It is characterized in that; The protection through S cleverly and removing in the preparation process; The salt-forming reaction of trivalent phosphine compound and halohydrocarbon can be effectively prevented, the N-heterocyclic carbine phosphine compound can be obtained smoothly.
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| CN110669078A (en) * | 2019-10-25 | 2020-01-10 | 南京林业大学 | Metal platinum complex based on axial chiral binaphthalene and preparation method and application thereof |
| CN111635432A (en) * | 2020-05-18 | 2020-09-08 | 南京工业大学 | Trost ligand with axial chiral binaphthyl skeleton and preparation method thereof |
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| CN115093440A (en) * | 2022-08-29 | 2022-09-23 | 南昌大学 | Method for cross coupling of hydrosilane compound and azacyclo-aromatic compound |
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| CN110669078B (en) * | 2019-10-25 | 2022-09-09 | 南京林业大学 | Metal platinum complex based on axial chiral binaphthalene and preparation method and application thereof |
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| CN115093440A (en) * | 2022-08-29 | 2022-09-23 | 南昌大学 | Method for cross coupling of hydrosilane compound and azacyclo-aromatic compound |
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