CN108947909A - A kind of chiral aza ring carbene precursor compound and its synthetic method with imidazolone skeleton - Google Patents
A kind of chiral aza ring carbene precursor compound and its synthetic method with imidazolone skeleton Download PDFInfo
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Abstract
The present invention discloses a kind of chiral aza ring carbene precursor compound and its synthetic method with imidazolone skeleton, the present invention is using cheap bromoacetyl bromide as raw material, pass through three-step reaction, the novel chiral benzimidazole carbene precursor compound of series structure succinctly can be effectively synthesized, to expand its application category in pharmaceutical intermediate synthetic reaction and organic asymmetric catalysis synthesis.
Description
Technical field
The present invention relates to organic synthesis fields, and in particular to a kind of chiral aza ring carbene precursor with imidazolone skeleton
Compound and its synthetic method.
Background technique
N-heterocyclic carbine (N-heterocyclic carbenes, NHCs) has become extremely important in current chemical field
Ligand be designed to the preparation of metal-organic complex, and then be widely used in homogeneous catalysis, pharmaceutical chemistry, asymmetric close
At and Material Field.Although Wanzlick andEarly in the last reagent sixties it has been reported that N-heterocyclic carbine, still
Until the isolated free carbenes of the seminars such as Bertrand and Arduengo and until obtain single crystal data, NHCs neck
The relevant research in domain just attracts wide public concern.From electrical angle, nitrogen heterocycle carbine ligand belongs to singlet Cabbeen, because with card
Guest carbon center sp2The lone pair electrons of hydridization can be stablized by the lone pair electrons of two adjacent nitrogen-atoms, and then be formed in Cabbeen
The p track of heart sky.Therefore, NHCs shows the electron-donating and weaker pi-electron acceptance of strong σ, so that they are very suitable into
It is applied to homogeneous catalysis for the substitute of Phosphine ligands.In addition, having benefited from excellent efficiency of the NHCs in terms of metal catalytic, accordingly
Chiral nitrogen heterocycle carbine ligand has also obtained significant progress.
The current NHC ligand that seminar is developed both at home and abroad, basic structural unit be based primarily upon pentacyclic imidazoles or
The structures such as person's glyoxalidine.In recent years, the more special nitrogen heterocycle carbine ligand of some skeleton structures is reported successively.Include
Not in the big ring azo-cycle carbenes of traditional penta azacyclo carbenes (including hexa-atomic NHCs ligand and seven yuan of NHCs ligands)
There is the nitrogen heterocycle carbine ligand of carbonyl functional group with skeleton.The latter one skeleton is due to special Electrical distribution by this
The concern of area research person.
2008, Lavigne et al. reported skeleton with the hexa-atomic of carbonyl functional group in American Chemical Society's meeting will for the first time
The synthesis of the rhodium complex of azepine carbenes, and its electrical property and structure feature are inquired into, structure is as follows.
Then (2009), the Research team report five yuan of similar Cabbeen rhodium complexes with imidazolone skeleton again
Synthesis, and it is prepared for its enol form isomer, specific structure is as follows.
The same year, Bielawski seminar are prepared for hexa-atomic Cabbeen free ligand and itself and iridium of the skeleton with carbonyl
Complex compound, and careful parsing is carried out to structure by single crystal diffraction, specific structure is as follows, and related research result is published in beauty
In state's Society will.
Then, which is prepared for the complex compound that same carbenes and metal rhodium are formed and the network formed with copper again
Object is closed, and is well used in olefin interconversion decomposition reaction.
And it is visited by comparing the structure and distribution of charges of hexa-atomic carbenes and the hexa-atomic carbenes with carbonyl
Begging for introduce in Cabbeen skeleton electrically influences brought by carbonyl.
Recently, the design of this seminar has synthesized the serial new chiral carbene precursor salt with dihydropyrimidinonesand skeleton, and
Medium enantioselectivity on the upper side, the chirality that building series plays a significant role are obtained in the not addition reaction of catalysis aromatic aldehyde
Diaryl secondary alcohols.
The development course of chiral carbenes of the skeleton with carbonyl is made a general survey of, which is still in the starting stage.Although such as
This, the unique electrical property that the carbenes of such skeleton are embodied novel framework characteristic makes it have very big attraction
Power and researching value.Therefore, the synthetic method tool of ligand and its metal complex of the new parent nucleus with carbonyl functional group is developed
It is significant, the connotation of carbene chemistry taxology itself can be not only enriched, and can apply to asymmetric reaction and reduction portion
The production cost of broad range drug synthesis intermediate.
Summary of the invention
The purpose of the present invention is designing a succinct organic synthesis route, a kind of chirality with imidazolone skeleton is proposed
Aza ring carbene precursor compound and its synthetic method, to expand it in pharmaceutical intermediate synthetic reaction and organic asymmetric conjunction
At the application category in reaction.Specific technical solution is as follows:
A kind of chiral aza ring carbene precursor compound with imidazolone skeleton, which is characterized in that the chirality azacyclo-
Carbene precursor compound are as follows:
Or its enantiomter:
Wherein, R1Selected from phenyl, benzyl, tert-butyl, isopropyl, methyl and isobutyl group；
R2 is selected from phenyl, 1- naphthalene, 2- naphthalene, benzyl, isopropyl, tert-butyl and cyclohexyl；
R3Selected from chloride ion, bromide ion, tetrafluoroborate ion and hexafluorophosphoricacid acid ions.
Further, the structure of the chirality aza ring carbene precursor compound is selected from:
A kind of synthetic method of chiral aza ring carbene precursor compound as described in claim 1, which is characterized in that should
Method includes the following steps:
(I) will carry out instead under triethylamine effect in aprotic solvent such as logical formula (I) compound represented and aromatic amine
It answers, then collection type (II) compound, reaction formula are as follows from reaction product:
(II) in aprotic solvent, will the amides compound as shown in general formula (II) and chiral primary amine alkali effect
Under reacted, then collection type (III) compound, reaction formula are as follows from reaction product:
(III), will the chiral diamine as shown in general formula (III), trimethyl orthoformate or orthoformic acid three in aprotic solvent
Ethyl ester is reacted under lewis acid effect, and then collection type (IV) compound, reaction formula are as follows from reaction product:
Further, in the step (I), the molar ratio of formula (I) compound and arylamine is 1.1:1, reaction temperature
It is 20~30 DEG C, the reaction time is 1~3 hour.
Further, in the step (II), reaction temperature is 20~30 DEG C, and the reaction time is 10~16 hours, formula
(II) compound, chiral primary amine, alkali molar ratio be 1:1.2:2.
Further, in the step (III), reaction temperature is 100~120 DEG C, and the reaction time is 8~12 hours, formula
(III) compound, orthoformate, lewis acidic molar ratio are 1:1:1~2.
Beneficial effects of the present invention are as follows:
Chiral nitrogen heterocycle carbine ligand with imidazolone skeleton is the research frontier of Organometallic Chemistry, due to
Imidazoles ring skeleton introduces carbonyl functional group, will significantly change distribution and the catalytic performance of the cloud density of such carbenes
Deng so that it has more unique property in catalysis reaction.The synthetic method of such ligand is rare, and the present invention is with cheap bromine
Acetyl bromide is raw material, by three-step reaction, succinctly can effectively synthesize the novel chiral aza ring carbene precursor salt of series structure,
And chiral centre can be introduced in N atom side chain.Such ligand can be used as ligand and metal center forms complex compound, urge in metal
Change in reaction system and show superior reactivity, and the catalysis for being expected to obtain high enantiomter in asymmetric reaction produces
Object.
Specific embodiment
Below according to preferred embodiment the present invention is described in detail, the objects and effects of the present invention be will become more apparent, with
Under in conjunction with the embodiments, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
The synthetic route of chiral aza ring carbene precursor compound of the invention is as follows:
Wherein, (I) is aromatic amine, triethylamine, methylene chloride；(II) chiral primary amine, alkali, tetrahydrofuran；(III) orthoformic acid
Triethyl or trimethyl orthoformate, ammonium salt (such as ammonium tetrafluoroborate, ammonium chloride).
The representative synthetic method (logical method 1) of compound ii:
Under nitrogen protection, 4mmol aromatic amine (1 equivalent), 8mmol triethylamine (2 equivalent) are dissolved in dry methylene chloride
It in (40mL), under condition of ice bath (0 DEG C), is added 4.4mmol compound (I) (1.1 equivalent), after being stirred at room temperature 3 hours, is added
Then the dilution of 20mL methylene chloride is added the washing of 30mL saturated ammonium chloride solution, separates organic layer, through saturated common salt water washing,
Organic layer is separated, filters evaporated under reduced pressure after anhydrous sodium sulfate is dry, mixture column chromatography for separation (PE:EA=10:1) obtains product
Ⅱ。
The representative synthetic method (logical method 2) of compound III:
Under nitrogen protection, 4.0mmol sodium hydride (2 equivalent) and 2.4mmol chiral primary amine (1.2 equivalent) are dissolved in 10mL's
THF solution is added dropwise to the THF solution (10mL) of 2.0mmol compound (II) (1 equivalent), stirs 14 hours at room temperature, reaction knot
Shu Hou is added the washing of 15mL saturated ammonium chloride solution, separates organic layer, through saturated common salt water washing, separates organic layer, anhydrous sulphur
Evaporated under reduced pressure is filtered after sour sodium is dry, mixture column chromatography for separation (PE:EA=8:1) obtains product III.
The representative synthetic method (logical method 3) of compounds Ⅳ:
1mmol compound III (1 equivalent), 1mmol triethyl orthoformate (1 equivalent) and 1mmol ammonium tetrafluoroborate are mixed,
It is reacted under 120 DEG C of heating conditions 12 hours, after reaction, by mixture column chromatography for separation (CH2Cl2:CH3OH=50:1~
20:1) obtain product IV.
Embodiment 1
The preparation and representation of compound ii -1:
Under nitrogen protection, by 4mmol trimethyl aniline (562 μ L, 4mmol) and 8mmol triethylamine (1112 μ L,
It 8mmol) is dissolved in dry methylene chloride (40mL), under condition of ice bath (0 DEG C), 1.07g compound (I) (4.4mmol) is added and exists
After being stirred at room temperature 3 hours, the dilution of 20mL methylene chloride is added, the washing of 30mL saturated ammonium chloride solution is then added, separates organic
Layer separates organic layer, filters evaporated under reduced pressure, mixture column chromatography for separation after anhydrous sodium sulfate is dry through saturated common salt water washing
(PE:EA=10:1) product II -1, yield 94% are obtained.
Embodiment 2
The preparation and representation of compound ii -2:
Preparation condition is the same as embodiment 1, yellow oil, yield 90%.
Embodiment 3
The preparation and representation of compound III -1:
Under nitrogen protection, sodium hydride (96mg, 4mmol) and chiral primary amine (309 μ L, 2.4mmol) are dissolved in the THF of 10mL
Solution is added dropwise to the THF solution (10mL) of compound (II -1) (596mg, 2.0mmol), stirs 14 hours at room temperature, reaction knot
Shu Hou is added the washing of 15mL saturated ammonium chloride solution, separates organic layer, through saturated common salt water washing, separates organic layer, anhydrous sulphur
Evaporated under reduced pressure is filtered after sour sodium is dry, mixture column chromatography for separation (PE:EA=8:1) obtains product III -1；Yield is 81%；1H
NMR(500MHz,CDCl3)δ:8.80(s,1H),7.37–7.30(m,4H),7.24–7.20(m,1H),6.87(s,2H),4.02
(q, J=6.7Hz, 1H), 2.25 (s, 3H), 2.13 (s, 6H), 1.41 (d, J=6.7Hz, 3H), 1.39 (s, 3H), 1.38 (s,
3H).
Embodiment 4
The preparation and representation of compound III -2:
Preparation condition is the same as embodiment 3, white solid, yield 79%；1H NMR(500MHz,CDCl3)δ:8.87(s,
1H), 7.33-7.27 (m, 4H), 7.24-7.20 (m, 1H), 6.88 (s, 2H), 3.72 (dd, J=8.1,5.7Hz, 1H), 2.26
(s, 3H), 2.14 (s, 6H), 1.82-1.63 (m, 2H), 1.35 (s, 3H), 1.30 (s, 3H), 0.79 (t, J=7.4Hz, 3H)
Embodiment 5
The preparation and representation of compound III -3:
Preparation condition is the same as embodiment 3, white solid, yield 72%；1H NMR(500MHz,CDCl3)δ:9.02(s,
1H),6.88(s,2H),2.79–2.72(m,1H),2.26(s,3H),2.18(s,6H),1.79–1.65(m,6H),1.54–
1.37 (m, 11H), 1.06 (d, J=6.5Hz, 3H)
Embodiment 6
The preparation and representation of compound III -4:
Preparation condition is the same as embodiment 3, white solid, yield 73%；1H NMR(500MHz,CDCl3)δ:9.09(s,
1H), 6.88 (s, 2H), 2.66 (q, J=6.4Hz, 1H), 2.26 (s, 3H), 2.18 (s, 6H), 1.47 (s, 3H), 1.43 (s,
3H), 1.08 (d, J=6.4Hz, 3H), 0.94 (s, 9H)
Embodiment 7
The preparation and representation of compound III -5:
Preparation condition is the same as embodiment 3, white solid, yield 75%；1H NMR(500MHz,CDCl3)δ:9.10(s,
1H),7.28–7.25(m,1H),7.18–7.16(m,2H),3.06–3.01(m,2H),2.78–2.73(m,1H),1.79–1.66
(m, 5H), 1.46 (s, 3H), 1.45 (s, 3H), 1.39-1.11 (m, 18H), 1.08 (d, J=6.5Hz, 3H)
Embodiment 8
The preparation and representation of compound III -6:
Preparation condition is the same as embodiment 3, white solid, yield 79%；1H NMR(500MHz,CDCl3)δ:9.17(s,
1H), 7.27-7.24 (m, 1H), 7.17 (d, J=7.7Hz, 2H), 3.03 (m, 2H), 2.67 (q, J=6.4Hz, 1H), 1.49
(s, 3H), 1.44 (s, 3H), 1.22 (d, J=6.9Hz, 6H), 1.19 (d, J=6.9Hz, 6H), 1.10 (d, J=6.4Hz,
3H),0.94(s,9H).
Embodiment 9
The preparation and representation of compound III -7:
Preparation condition is the same as embodiment 3, white solid, yield 81%；1H NMR(500MHz,CDCl3)δ:9.09(s,
1H),7.40–7.38(m,1H),7.25–7.24(m,1H),7.19–7.10(m,5H),4.12(m,1H),3.03–2.98(m,
2H),2.86–2.80(m,1H),2.75–2.69(m,1H),2.00–1.79(m,4H),1.61(s,3H),1.60(s,3H),
1.48–1.33(m,1H),1.19–1.16(m,6H).
Embodiment 10
The preparation and representation of compounds Ⅳ -1:
By compound III -1 (338mg, 1mmol), triethyl orthoformate (148mg, 1mmol) and ammonium tetrafluoroborate
(126mg, 1.2mmol) mixing, reacts 12 hours under 120 DEG C of heating conditions, after reaction, by mixture column chromatography for separation
(CH2Cl2:CH3OH=50:1~20:1) obtain product IV -1, yield 70%.
Embodiment 11
The preparation and representation of compounds Ⅳ -2:
Preparation condition is the same as embodiment 10, white solid, yield 69%；1H NMR(500MHz,CDCl3)δ:8.59(s,
1H), 7.38 (t, J=5.8Hz, 2H), 7.35-7.31 (m, 3H), 6.82 (s, 2H), 4.57 (t, J=7.9Hz, 1H), 2.23
(s, 3H), 2.10 (s, 6H), 1.67 (s, 3H), 1.54 (s, 3H), 1.26 (s, 2H), 1.06 (t, J=7.3Hz, 3H)
Embodiment 12
The preparation and representation of compounds Ⅳ -3:
Preparation condition is the same as embodiment 10, white solid, yield 73%；1H NMR(500MHz,CDCl3)δ:。1H NMR
(500MHz,CDCl3)δ:9.08(s,1H),7.02(s,1H),7.00(s,1H),3.68(m,1H),2.32(s,3H),2.17
(s,3H),2.12(s,3H),2.09–1.60(m,20H).
Embodiment 13
The preparation and representation of compounds Ⅳ -4:
Preparation condition is the same as embodiment 10, white solid, yield 68%；1H NMR(500MHz,CDCl3)δ:9.57(s,
1H), 7.05 (s, 1H), 6.98 (s, 1H), 3.79 (q, J=7.1Hz, 1H), 2.32 (s, 3H), 2.20 (s, 3H), 2.12 (s,
3H), 1.81 (s, 3H), 1.73 (s, 3H), 1.69 (d, J=7.1Hz, 3H), 1.13 (s, 9H)
Embodiment 14
The preparation and representation of compounds Ⅳ -5:
Preparation condition is the same as embodiment 10, white solid, yield 72%；1H NMR(500MHz,CDCl3)δ:9.76(s,
1H), 7.52 (t, J=7.8Hz, 1H), 7.30 (d, J=3.5Hz, 1H), 7.15 (d, J=7.7Hz, 1H), 3.78 (m, 1H),
2.54 (m, 1H), 2.45 (m, 1H), 2.09-1.91 (m, 4H) 1.80-1.73 (m, 7H), 1.64 (d, J=2.5Hz, 3H),
1.60–1.16(m,18H).
Embodiment 15
The preparation and representation of compounds Ⅳ -6:
Preparation condition is the same as embodiment 10, white solid, yield 65%；1H NMR(500MHz,CDCl3)δ:9.70(s,
1H), 7.53 (t, J=7.8Hz, 1H), 7.34 (d, J=7.9Hz, 1H), 7.28 (d, J=7.9Hz, 1H), 3.87 (q, J=
7.1Hz, 1H), 2.60 (m, 1H), 2.44 (m, 1H), 1.84 (s, 3H), 1.76 (s, 3H), 1.71 (d, J=7.1Hz, 3H),
1.35–1.12(m,21H)。
Embodiment 16
The preparation and representation of compounds Ⅳ -7:
Preparation condition is the same as embodiment 10, white solid, yield 78%；1H NMR(500MHz,CDCl3)δ:8.57(s,
1H),7.38–7.14(m,7H),3.55–3.50(m,2H),3.15–2.82(m,5H),1.75(s,6H),1.46–1.12(m,
16H).
It will appreciated by the skilled person that being not used to limit the foregoing is merely the preferred embodiment of invention
System invention, although invention is described in detail referring to previous examples, for those skilled in the art, still
It can modify to the technical solution of aforementioned each case history or equivalent replacement of some of the technical features.It is all
Within the spirit and principle of invention, modification, equivalent replacement for being made etc. be should be included within the protection scope of invention.
Claims (6)
1. a kind of chiral aza ring carbene precursor compound with imidazolone skeleton, which is characterized in that the chirality azacyclo- card
Guest's precursor compound are as follows:
Or its enantiomter:
Wherein, R1Selected from phenyl, benzyl, tert-butyl, isopropyl, methyl and isobutyl group.
R2 is selected from phenyl, 1- naphthalene, 2- naphthalene, benzyl, isopropyl, tert-butyl and cyclohexyl.
R3Selected from chloride ion, bromide ion, tetrafluoroborate ion and hexafluorophosphoricacid acid ions.
2. the chiral aza ring carbene precursor compound according to claim 1 with imidazolone skeleton, which is characterized in that
The structure of the chirality aza ring carbene precursor compound is selected from:
3. a kind of synthetic method of chiral aza ring carbene precursor compound as described in claim 1, which is characterized in that the party
Method includes the following steps:
(I) will react under triethylamine effect in aprotic solvent such as logical formula (I) compound represented and aromatic amine,
Then collection type (II) compound, reaction formula are as follows from reaction product:
(II) in aprotic solvent, will the amides compound as shown in general formula (II) and chiral primary amine in the presence of alkali into
Row reaction, then collection type (III) compound, reaction formula are as follows from reaction product:
(III) in aprotic solvent, will chiral diamine, trimethyl orthoformate or triethyl orthoformate as shown in general formula (III),
It is reacted under lewis acid effect, then collection type (IV) compound, reaction formula are as follows from reaction product:
。
4. synthetic method according to claim 3, which is characterized in that in the step (I), formula (I) compound and virtue
The molar ratio of base amine is 1.1:1, and reaction temperature is 20~30 DEG C, and the reaction time is 1~3 hour.
5. synthetic method according to claim 3 or 4, which is characterized in that in the step (II), reaction temperature 20
~30 DEG C, the reaction time be 10~16 hours, formula (II) compound, chiral primary amine, alkali molar ratio be 1:1.2:2.
6. synthetic method according to claim 5, which is characterized in that in the step (III), reaction temperature be 100~
120 DEG C, the reaction time is 8~12 hours, and formula (III) compound, orthoformate, lewis acidic molar ratio are 1:1:1~2.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102083798A (en) * | 2008-04-09 | 2011-06-01 | 马特里亚公司 | Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone |
| CN105772094A (en) * | 2016-04-21 | 2016-07-20 | 上海化工研究院 | Chiral nitrogen heterocycle carbene type catalyst and application thereof |
| CN108456172A (en) * | 2018-04-20 | 2018-08-28 | 浙江大学城市学院 | A kind of chiral aza ring carbene precursor compound and its preparation method and application with benzimidazole skeleton |
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2018
- 2018-09-04 CN CN201811025530.6A patent/CN108947909B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102083798A (en) * | 2008-04-09 | 2011-06-01 | 马特里亚公司 | Ruthenium olefin metathesis catalysts bearing N-heterocyclic carbene ligands with substituted backbone |
| CN105772094A (en) * | 2016-04-21 | 2016-07-20 | 上海化工研究院 | Chiral nitrogen heterocycle carbene type catalyst and application thereof |
| CN108456172A (en) * | 2018-04-20 | 2018-08-28 | 浙江大学城市学院 | A kind of chiral aza ring carbene precursor compound and its preparation method and application with benzimidazole skeleton |
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| Title |
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| SARAH M. BRONNER，ET AL.: "Ru-based Z-selective metathesis catalysts with modified cyclometalated carbene ligands", 《CHEM. SCI.》 * |
| 周碧辉: "新型手性大环卡宾配体的设计合成及其在催化反应中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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