CN103012498B - Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction - Google Patents
Chiral ferrocene tridentate ligand and preparation method thereof and the application in catalysis asymmetry hydrogenation reaction Download PDFInfo
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- CN103012498B CN103012498B CN201310007046.1A CN201310007046A CN103012498B CN 103012498 B CN103012498 B CN 103012498B CN 201310007046 A CN201310007046 A CN 201310007046A CN 103012498 B CN103012498 B CN 103012498B
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Abstract
The invention discloses the ferrocene tridentate ligand shown in general structure (I) that a class has face chirality and carbon chirality concurrently, wherein, R
1for aryl or C
1~ C
6alkyl; R
2for C
1~ C
6alkyl, n=1 ~ 4, or R
2do not exist.Ferrocene tridentate ligand of the present invention with chirality Ugi ' s amine for raw material after s-butyl lithium lithiumation with R
1 2pCl coupling, aceticanhydride esterification, last and aminomethyl-pyridine or replacement aminomethyl-pyridine generation nucleophilic substitution reaction synthesizes and obtains.Chiral ferrocene ligands of the present invention has very high catalytic activity, has outstanding stereoselectivity and very high catalytic activity when its Ir complex compound catalyst is used for the asymmetric hydrogenation of prochiral ketone.
Description
Technical field
The present invention relates to the synthesis of a class chipal compounds, be specifically related to a class and have the synthesis of the ferrocene tridentate ligand of face chirality and carbon chirality and the application in prochiral ketone catalysis asymmetric hydrogenation thereof concurrently, belong to technical field of organic synthesis.
Background technology
The dive hydrogenation of the unsaturated substrate of chirality (ketone, imines, alkene etc.) of chiral ligand and transition metal complex catalyst catalysis is the important channel obtaining various chiral material.The key of asymmetric catalysis is design and the synthesis of the catalyzer of high reactivity and highly-solid selectively, and chiral ligand is the root of chiral catalyst asymmetric induction and zinc bromide.In recent decades, people have designed and synthesized the part of many high catalytic activities and highly-solid selectively, and what have is applied to suitability for industrialized production.As DIOP (Kagan, H.B.; Dang, T.P.
chem.Commun. 1971, 481), BINAP (Yasuda, A.; Tayaka, H.; Miyashita, A.; Toriumi, K.; Ito, T.; SouchiT.; NoyoriR.
j.Am.Chem.Soc. 1980, 102,7932), DuPHOS (Burk, M.J.; Feaster, J.E.; Harlow, R.L.
organometallics. 1990, 9,2653), [((
s)-Tol-BINAP) ((
s,
s)-DEPEN)] (Noyori, R.
angew.Chem.Int.Ed. 1998, 37,1703) etc.Chiral ferrocene ligands iridium catalyst Ir-Xyliphos (Blaser, H.U.
adv.Synth.Catal. 2002, 344,17) and the asymmetric hydrogenation TON value of catalyze imine is up to 10
6, Zhou Qilin seminar of Nankai University report volution tridentate ligand iridium catalyst Ir-SpiroPAP (Xie, J.H.; Liu, X.Y.; Xie, J.B.; Wang, L.X.; Zhou, Q.L.
angew.Chem.Int.Ed. 2011, 50,7329) and TON value in the asymmetric hydrogenation of catalysis ketone is up to 4.5 × 10
6.Although asymmetric catalytic hydrogenation research is achieving many achievements attracted people's attention in recent decades, but the catalyzer of catalytic activity high (TON value reaches 1,000,000) still cans be counted on one's fingers, thus design and development more efficient and the new chiral ligand of practicality and catalyzer remains the important content of asymmetric synthesis research.
Summary of the invention
The object of the present invention is to provide that a class synthesis step is easy, the face that has concurrently the chirality of good stability and the ferrocene tridentate ligand of carbon chirality, the structure of this kind of part is based on Ir-Xyliphos and Ir-SpiroPAP chiral ligand structure activity study, introduces the ferrocene structural unit of novel face chirality in the structure.
Another object of the present invention is to the preparation method that above-mentioned chiral ligand is provided.
A further object of the invention is the application of iridium complex catalyzer in the asymmetric catalytic hydrogenation of prochiral ketone providing above-mentioned tridentate ligand.
Implementation procedure of the present invention is as follows:
General structure (
i) shown in ferrocene tridentate ligand:
Wherein, R
1for C
1~ C
6alkyl or aryl; R
2for C
1~ C
6alkyl, n=1 ~ 4, or R
2do not exist.
Described aryl refers to any from the functional group that simple aromatic nucleus derives or substituting group, comprises the phenyl, 1-naphthyl (or Alpha-Naphthyl), 2-naphthyl etc. of phenyl, the replacement of C1-C5 alkyl.
General structure (
i) be
rcarbon chirality and
sface chiral tridentate part, or
scarbon chirality and
rface chiral tridentate part, or racemic tridentate ligand.
The preparation method of above-mentioned ferrocene tridentate ligand, comprise the steps: with chirality Ugi ' s amine for raw material after s-butyl lithium lithiumation with R
1 2pCl coupling, aceticanhydride esterification, last and aminomethyl-pyridine or pyridine ring are by R
2the aminomethyl-pyridine generation nucleophilic substitution reaction synthesis replaced obtains, R
1for the alkyl of aryl or C1 ~ C6, R
2for the alkyl of C1 ~ C6.
The present invention also include general structure (
i) shown in the complex of iridium of ferrocene tridentate ligand.
Ferrocene tridentate ligand of the present invention is applied in prochiral ketone catalysis asymmetric hydrogenation, specifically, the present invention with chirality Ugi ' s amine (
a) be starting raw material, first after s-butyl lithium lithiumation with R
1 2pCl reaction obtains product in 1 ~ 5 hour
b, temperature of reaction-20 ~ 50 DEG C, reaction solvent is methyl tertiary butyl ether; Then stir in aceticanhydride and obtain for 1 ~ 24 hour
c, temperature of reaction 0 ~ 150 DEG C; Finally react with the aminomethyl-pyridine of aminomethyl-pyridine or replacement in the mixed solvent of methyl alcohol and tetrahydrofuran (THF) within 1 ~ 24 hour, obtain part (
i), temperature of reaction 0 ~ 100 DEG C.
Chiral ferrocene ligands of the present invention has face chirality and carbon chirality simultaneously, its comprise from
rthe face chirality of configuration Ugi ' s amine synthesis is
sconfiguration (
r,
s)-part and from
sthe synthesis of configuration Ugi ' s amine (
s,
r)-part.The part of different configuration has identical chemical structure of general formula, but has different three-dimensional arrangements and opticity.
Chiral ferrocene ligands of the present invention is the part with very high catalytic activity, its Ir complex compound catalyst has outstanding stereoselectivity and very high catalytic activity when being used for the asymmetric hydrogenation of prochiral ketone, the mol ratio of prochiral ketone and chiral ligand (I) is 1000 ~ 1000000, temperature of reaction 0 ~ 60 DEG C, hydrogen pressure is 1 ~ 150atm, reaction times is 1 ~ 48h, and reaction solvent is the alcohol organic solvent such as methyl alcohol, its reaction expression:
R
1for C
1~ C
6alkyl or aryl; N=0 ~ 4, R
2for C
1~ C
6alkyl; R
3, R
4independently selected from C
1~ C
6alkyl, cycloalkyl or aryl, R
3, R
4not identical.
Chiral ferrocene ligands of the present invention has very high catalytic activity, has outstanding stereoselectivity and very high catalytic activity when its Ir complex compound catalyst is used for the asymmetric hydrogenation of prochiral ketone.
Embodiment
embodiment 1 is synthesized (
r
c
,
s
fe
)-1-[(2-biphenyl phosphino-) ferrocenyl]-
n,
n-dimethyl amine
Take (
r)-Ugi ' s amine (2.57g, 10mmol) adds in the Schlenk reaction tubes of 50mL, vacuumize/inflated with nitrogen three times, inject dried methyl tertiary butyl ether 15mL, be stirred to dissolving, slowly inject 1.3M
s-BuLi (9.2mL, 12mmol), react at ambient temperature and generate orange floss in 1 hour, more slowly inject the diphenyl phosphine chloride (1.8mL being dissolved in 10mL methyl tertiary butyl ether, 10mmol), to rise to 40 DEG C of reactions 4 little of reacting completely for temperature.Cross and filter insolubles, after solvent evaporated, column chromatography obtains product 3.1g, with dehydrated alcohol recrystallization 1.8g, and productive rate 40.8%.
mp141-143℃;
-350.9(c=0.25,CHCl
3);
1HNMR(500Hz,CDCl
3)：δ7.62-7.56(m,2H),7.37-7.32(m,3H),7.22-7.14(m,5H),4.37(s,1H),4.25-4.24(m,1H),4.16-4.14(dd,
J 1 =2.5,
J 2 =2.5Hz,1H),3.94(s,5H),3.86(s,1H),1.77(s,6H),1.27-1.26(d,J=7Hz,3H).
the 2-in-1 one-tenth of embodiment (
r
c
,
s
fe
)-1-[2-bis-(3,5-3,5-dimethylphenyl) phosphino-] ferrocenyl-
n,
n-dimethyl amine
Preparation method, with embodiment 1, obtains orange oily matter 2.2g, productive rate 44.2%.
-278.5(c=0.25,CHCl
3);
1HNMR(500Hz,CDCl
3)δ7.25-7.23(m,2H),6.98(s,1H),6.80-6.78(m,3H),4.35(s,1H),4.23-4.22(m,1H),4.10-4.08(dd,
J 1 =2.5,
J 2 =2.5Hz,1H),3.92(s,5H),3.87(s,1H),2.32(s,6H),2.18(s,6H),1.81(s,6H),1.28-1.27(d,J=7Hz,3H).
embodiment 3 synthetic ligands (
r
c
,
s
fe
)-1-(2-diphenylphosphino) ferrocenyl)-
n-(pyridyl-2-methyl) ethamine
Take (
r)-
n,
n-dimethyl-1-[(
s)-2-(diphenylphosphino) ferrocenyl] ethamine (0.882g, 2mmol) adds in 50mLSchlenk reaction tubes, vacuumizes/inflated with nitrogen three times, injects 15mL aceticanhydride, stirring at ambient temperature spends the night to reaction terminates.Decompression is by solvent evaporate to dryness, and gained acetic ester solid product directly carries out the next step.Add in 50mL there-necked flask by above-mentioned gained solid, the mixing solutions (1:1) first adding 10mL methyl alcohol and tetrahydrofuran (THF) is stirred to and dissolves completely, then adds 0.5mL2-aminomethyl-pyridine, and back flow reaction 10 is little of reacting completely.Be spin-dried for after extracted with diethyl ether, anhydrous sodium sulfate drying after frozen water cancellation, column chromatography obtains product 0.51g, productive rate 47.2%.
m.p.137.2～139.5℃，
1HNMR(400MHz,CDCl
3)
,δ8.34-8.13(d,
J=4.4Hz,1H),7.48-7.40(m,3H),7.39-6.80(m,9H),6.62-6.45(d,
J=7.6Hz,1H),4.52-4.50(s,1H),4.35-4.25(s,1H),4.25-4.15(dd,
J 1 =2.4Hz,
J 2 =2.4Hz,1H),4.15-3.90(s,5H),3.85-3.77(s,1H),3.70-3.55(d,
J=2Hz,2H),2.00-2.10(s,1H),1.65-1.50(d,
J=6.4Hz,3H).
embodiment 4 synthetic ligands (
r
c
,
s
fe
)-1-(2-diphenylphosphino) ferrocenyl)-
n-(quinolyl-2-methyl) ethamine
Preparation method, with embodiment 3, obtains yellow blister solid 0.59g, productive rate 53.2%.
-276.8(c=0.25,CH
2Cl
2);
1HNMR(500Hz,CDCl
3)δ7.93-7.85(d,
J=8.5Hz,1H),7.84-7.78(d,
J=8.5Hz,1H),7.74-7.67(d,
J=8Hz,1H),7.65-7.59(m,1H),7.58-7.51(m,2H),7.49-7.42(m,1H),7.40-7.33(m,3H),7.25-7.20(m,1H),7.14-7.06(m,2H),7.03-6.98(m,1H),6.79-6.74(d,
J=8.5Hz,1H),4.58(s,1H),4.34(s,1H),4.33-4.25(d,
J=3.5Hz,1H),4.01(s,5H),3.90-3.80(m,3H),1.65-1.58(d,
J=6Hz,3H).
embodiment 5 synthetic ligands (
r
c
,
s
fe
)-1-(2-diphenylphosphino) ferrocenyl)-
n-(3-pyridyl-2-methyl) ethamine
Preparation method, with embodiment 3, obtains orange solid 0.62g, productive rate 60.1%.
mp103.2-104℃;
-353.6(c=0.25,CH
2Cl
2);
1HNMR(500Hz,CDCl
3)δ8.10-8.05(d,
J=4Hz,1H),7.60-7.52(m,2H),7.40-7.32(m,3H),7.23-7.16(m,3H),7.13-7.03(m,3H),6.92-6.87(m,1H),4.57(s,1H),4.33-.4.30(m,1H),4.18-4.12(dd,
J 1 =3,
J 2 =2.5Hz,1H),3.97(s,5H),3.88-3.84(m,1H),3.78-3.63(d,
J=14Hz,1H),3.54-3.49(d,
J=14Hz,1H),1.97(s,3H),1.66-1.61(d,
J=6.5Hz,3H).
embodiment 6 synthetic ligands (
r
c
,
s
fe
)-1-(2-diphenylphosphino) ferrocenyl)-
n-(6-pyridyl-2-methyl) ethamine
Preparation method, with embodiment 3, obtains the sticky solid 0.65g of orange, productive rate 63.2%.
-243.8(c=0.65,CH
2Cl
2);
1HNMR(500Hz,CDCl
3)δ7.56-7.50(m,2H),7.40-7.33(m,3H),7.28-7.20(m,3H),7.17-7.10(m,3H),6.88-6.82(d,
J=7.5Hz,1H),6.36-6.30(d,
J=7.5Hz,1H),4.53(s,1H),4.33-4.28(m,1H),4.25-4.17(m,1H),4.00(s,5H),3.85-3.80(m,1H),3.62(s,1H),2.41(s,3H),1.57-1.53(d,
J=6.5Hz,3H).
embodiment 7 synthetic ligands (
r
c
,
s
fe
)-1-[2-(two (3,5-3,5-dimethylphenyl) phosphino-) ferrocenyl]-
n-(6-pyridyl-2-methyl) ethamine
Preparation method, with embodiment 3, obtains the sticky solid 0.52g of orange, productive rate 45.5%.
-262.4(c=0.25,CH
2Cl
2);
1HNMR(500Hz,CDCl
3)δ7.28-7.23(m,1H),7.22-7.17(d,
J=8.5Hz,2H),7.04(s,1H),6.92-6.84(m,3H),6.74(s,1H),6.32-6.28(d,
J=8Hz,1H),4.55(s,1H),4.34-4.30(m,1H),4.29-4.22(dd,
J=3,3Hz,1H),4.08(s,5H),3.87-3.82(m,1H),3.68-3.58(dd,
J=14.5,14.5Hz,2H),2.47(s,3H),2.35(s,6H),2.11(s,6H),1.61-1.56(d,
J=6.5Hz,3H).
the asymmetric hydrogenation of embodiment 8 prochiral ketone
R
1for C
1~ C
6alkyl or aryl; N=0 ~ 4, R
2for C
1~ C
6alkyl; R
3, R
4independently selected from C
1~ C
6alkyl, cycloalkyl or aryl, R
3, R
4not identical.
Take part (
r c,
s fe)-1-[2-(two (3,5-3,5-dimethylphenyl) phosphino-) ferrocenyl]-
n-(6-pyridyl-2-methyl) ethamine (12.6mg, 0.022mmol), [Ir (COD) Cl]
2(7.32mg, 1mmol) adds in 25mLSchlenk reaction tubes, vacuumizes/inflated with nitrogen three times, injects the dehydrated alcohol of 2mL through nitrogen replacement, and stirring at room temperature 1 hour is for subsequent use.By methyl phenyl ketone (4.8g, 40mmol) add in 100mL autoclave, add the dehydrated alcohol of 30mL through nitrogen replacement, again above-mentioned reaction solution is added in reactor, after hydrogen exchange three times, pressure is risen to 20atm, stirred at ambient temperature 24 hours, TLC display react completely, column chromatography obtain weak yellow liquid product (
r)-1-phenylethyl alcohol 2.2g, productive rate 90.9%,
eevalue 78%.
Claims (8)
1. general structure (
i) shown in compound:
Wherein, R
1for aryl or C
1~ C
6alkyl; R
2for C
1~ C
6alkyl, n=1 ~ 4, or R
2do not exist.
2. compound according to claim 1, is characterized in that: general structure (
i) shown in compound be
rcarbon chirality and
sface chiral tridentate part, or
scarbon chirality and
rface chiral tridentate part, or racemic tridentate ligand.
3. the preparation method of compound described in claim 1, it is characterized in that comprising the steps: with chirality Ugi ' s amine for raw material after s-butyl lithium lithiumation with R
1 2pCl coupling, aceticanhydride esterification, last and pyridine ring is by R
2the aminomethyl-pyridine generation nucleophilic substitution reaction synthesis replaced obtains, and reaction formula is as follows,
R
1for the alkyl of aryl or C1 ~ C6, R
2for the alkyl of C1 ~ C6, n=1 ~ 4, or R
2do not exist.
4. the complex of iridium containing compound described in claim 1.
5. the application of compound described in claim 1 in prochiral ketone catalysis asymmetric hydrogenation.
6. apply according to claim 5, it is characterized in that: general structure (
i) shown in compound and transition metal iridium in-situ preparation metal complex catalyst after for the hydrogenation of catalysis prochiral ketone.
7. apply according to claim 6, it is characterized in that: prochiral ketone and general structure (
i) shown in the mol ratio of compound be 1000 ~ 1000000, temperature of reaction 0 ~ 60 DEG C, hydrogen pressure is 1 ~ 150atm, and the reaction times is 1 ~ 48h.
8. apply according to claim 7, it is characterized in that catalyzed reaction formula is as follows:
R
1for aryl or C
1~ C
6alkyl, R
2for C
1~ C
6alkyl, n=1 ~ 4, or R
2do not exist; R
3, R
4independently selected from C
1~ C
6alkyl, cycloalkyl or aryl, R
3, R
4not identical.
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| CN103831132A (en) * | 2014-02-25 | 2014-06-04 | 中国人民解放军第四军医大学 | Double-function square amide-phosphine organic catalyst based on ferrocene skeleton, preparation method and application of catalyst |
| CN103831133A (en) * | 2014-02-25 | 2014-06-04 | 中国人民解放军第四军医大学 | Bi-functional phosphine thiourea organic catalyst based on ferrocene skeleton as well as preparation method and application thereof |
| CN104592313B (en) * | 2014-12-30 | 2017-08-25 | 陕西师范大学 | Difunctional hydrogen bond organic catalyst based on ferrocene and its preparation method and application |
| CN105153229B (en) * | 2015-06-18 | 2017-12-08 | 武汉凯特立斯科技有限公司 | A kind of chiral tridentate PNN parts and its application in asymmetric hydrogenation |
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| CN107522751B (en) * | 2016-06-21 | 2020-01-21 | 中国科学院大连化学物理研究所 | High-steric-hindrance chiral ferrocene P, N, N ligand, preparation method and application |
| CN108101785A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that iridium catalysis asymmetric hydrogenation prepares chiral beta-hydroxy ester |
| CN110183498B (en) * | 2019-06-17 | 2022-04-29 | 浙江工业大学 | Chiral ferrocene phosphine nitrogen tridentate ligand and preparation method and application thereof |
| CN112300220B (en) * | 2020-11-11 | 2023-04-18 | 武汉纺织大学 | Chiral ferrocene P, N ligand derivative and preparation method and application thereof |
| CN113004341B (en) * | 2021-03-08 | 2023-08-01 | 洛阳师范学院 | PNO ligand containing facial chiral ferrocene and axial chiral diphenol and application thereof |
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