CN103102485B - Chiral ferrocene methylene aza-small cyclic amino alcohol ligand as well as synthetic method and application thereof - Google Patents
Chiral ferrocene methylene aza-small cyclic amino alcohol ligand as well as synthetic method and application thereof Download PDFInfo
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- CN103102485B CN103102485B CN201310037844.9A CN201310037844A CN103102485B CN 103102485 B CN103102485 B CN 103102485B CN 201310037844 A CN201310037844 A CN 201310037844A CN 103102485 B CN103102485 B CN 103102485B
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Abstract
The invention discloses a synthetic method of a chiral ferrocene methylene aza-small cyclic amino alcohol ligand loaded with polyethylene glycol and aromatic aldehyde asymmetric ethylation reaction catalyzed by the chiral ferrocene methylene aza-small cyclic amino alcohol ligand. The ligand is manufactured by loading polyethylene glycol to the chiral ferrocene methylene aza-small cyclic amino alcohol ligand by means of covalent bond. The ligand has the characteristics of easily availability and simplicity in raw materials, convenience in the synthetic method, high activity, high unsymmetrical selectivity, convenience in recovery, repeated utilization and the like.
Description
Technical field
The present invention relates to a kind of chiral ferrocene methylene radical azepine little ring amino alcohol ligands preparation method and use.
Background technology
The asymmetric reduction reaction of dialkyl group zinc to aldehyde is one of a kind of effective ways of growth that carbon carbon is good for.In the presence of chiral ligand, the asymmetric nucleophilic addition of alkyl metal cpd to carbonyl compound is one of reaction the most widely of research, is also one of effective ways preparing chiral alcohol.
From 1991, since the Trost chemist of the U.S. proposes this concept of " Atom economy " on Science, Green Chemistry is just flourish as an emerging chemical branch, so the green material in searching chemical reaction, green reaction process, green product is the inexorable trend of chemical developer.Wherein for the use of green material, polyoxyethylene glycol is good selection, because it is cheap and easy to get and nontoxic, is easy to modify and have special solvability.1993, Bergbreiter has synthesized the hydrogenation reaction (Bergbreiter of polyoxyethylene glycol complex compound for catalyzing propone alcohol of rhodium, D E, Zhang L, Mariagnanam V M. J. Am. Chem. Soc. 1993,115:9295 ~ 9296.), thus, the catalyzer of polyoxyethylene glycol load just arrived extensive concern.Subsequently, the catalyzer of polyoxyethylene glycol load is just usually applied quickly at epoxidation reaction (Kumaraswamy G. J. Mol. Catal. A:Chem., 2005, 230:59 ~ 67.), ciprofloxacin eye drops reaction (Zhang J L, Che C M. Org. Lett., 2002, 4:1911 ~ 1914), reduction hydrogenation (Guerreiro P, Ratovelomanana V V, Gen ê t J P, et al. Tetrahedron Lett., 2001, 42:3423 ~ 3426.), asymmetric reduction reaction, DA reacts (Annunziata R, Benaglia M, Cinquini M, et al. J. Org. Chem., 2001, 66:2932 ~ 2936.), allyl group alkylated reaction (Bandini M, Benaglia M, Quinto T. et al. AdV. Synth. Catal. 2006, 348:1521 ~ 1527.) and Alold reaction (Benaglia M, Celentano G. AdV. Synth. Catal. 2002, 344:533 ~ 542.) etc., in these reactions, the catalyst recovery method of polyoxyethylene glycol load is easy and can repeatedly recycle, and the very high productive rate obtained and good stereoselectivity.
1984, Oguni and Omi employed the addition reaction that amino alcohol ligands different in a large number comes catalysis phenyl aldehyde and zinc ethyl, obtained the ee value (Oguni N, Omi T. Tetrahedron Lett. 1984,25,2823 ~ 2824.) of 49%.People have synthesized various part and have reacted for this type of subsequently, obtain the enantioselectivity (Soai K, Niwa S. Chem. Rev. 1992,92,833 ~ 856.) up to more than 99%.But because many chiral catalyst synthesis steps used are more, cost is comparatively large, is difficult to obtain, general recovery is got up also more difficult, and some catalyzer is even poisonous, if directly emitted, the pollution of environment will certainly be caused, also do not meet the requirement of Green Chemistry simultaneously.In order to address these problems, polyoxyethylene glycol is loaded on chiral ligand, catalysis asymmetric reduction reaction is by significant.
Summary of the invention
The object of the invention is to provide a kind of synthetic method of the little ring amino alcohol ligands of chiral ferrocene methylene radical azepine and the application in the Unsymmetrical alkylation of aldehyde thereof of polyoxyethylene glycol load of recyclable recycling, and such part can reclaim easily.
The structural formula of the chiral ferrocene methylene radical azepine little ring amino alcohol ligands of polyoxyethylene glycol load of the present invention is as follows:
The route of the synthetic method of the chiral ferrocene methylene radical azepine little ring amino alcohol ligands of polyoxyethylene glycol load of the present invention is as follows:
The present invention is to be cheaply easy to get
l-Serine is starting raw material, by six step chemical reactions, prepares the little ring amino alcohol ligands 5 of chiral ferrocene methylene radical azepine of polyoxyethylene glycol load, wherein from the 2-in-1 one-tenth of ferrocene methylene radical aziridinyl methyl-formiate
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol 3, from 3 synthesis
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol 4, from 4 synthesis 5, this three steps synthesis step is key component of the present invention.
Its concrete steps are as follows:
(1) ferrocene methylene radical aziridinyl methyl-formiate and grignard reagent react, under the condition of 0-10 DEG C, the reaction times is 40-60 h, and described ferrocene methylene radical aziridinyl methyl-formiate is 1:2-8 with the ratio of the amount of substance of Grignard reagent, obtains
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol;
(2)
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol and TBAF react, and react 1-3 h under the condition of 10-30 DEG C, described in
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol are 1:2-4 with the ratio of the amount of substance of TBAF, and deprotection obtains
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol;
(3)
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid's base methyl alcohol and molecular weight be 2000 polyoxyethylene glycol react, under the condition of 60 ~ 70 DEG C, react 3-5h, described in
nthe ratio that-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol and molecular weight are the amount of substances of the polyoxyethylene glycol of 2000 is 1:1-3, obtains a kind of little ring amino alcohol ligands of chiral ferrocene methylene radical azepine of polyoxyethylene glycol load.
The methyl-formiate of ferrocene methylene radical aziridinyl described in described step (1) is preferably 1:3-5 with the ratio of the amount of substance of Grignard reagent.
In described step (2)
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol are preferably 1:3 with the ratio of the amount of substance of TBAF.
In described step (3), reaction is carried out in solvent DMF, described in
nthe ratio that-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol and molecular weight are the amount of substances of the polyoxyethylene glycol of 2000 is preferably 1:2.
The chiral ferrocene methylene radical azepine little ring amino alcohol ligands of described polyoxyethylene glycol load is applied to the catalyzer of the asymmetric ethylation reaction of all kinds of aromatic aldehyde.
The chiral ferrocene methylene radical azepine little ring amino alcohol ligands 5 of polyoxyethylene glycol load of the present invention may be used for the asymmetric ethylation reaction of the various aromatic aldehyde of catalysis.
The asymmetric ethylation reaction of aromatic aldehyde:
The asymmetric ethylation reaction of the various aromatic aldehydes utilizing this type of part to carry out, all achieves extraordinary result as table 1.It is as shown in table 2 that part of the present invention can reuse situation:
The asymmetric ethylation reaction of the various aromatic aldehyde of table 1
| Sequence number | Part | Aldehyde | Productive rate/% | Ee value/% | Absolute configuration |
| 1 | 7 | Ph | 88 | 92 | S |
| 2 | 7 | 4–CH 3Ph | 67 | 88 | S |
| 3 | 7 | 4–CH 3OPh | 63 | 85 | S |
| 4 | 7 | 3–CH 3OPh | 65 | 81 | S |
| 5 | 7 | 4–ClPh | 76 | 87 | S |
| 6 | 7 | 2–ClPh | 84 | 83 | S |
| 7 | 7 | FcCHO | 77 | 85 | S |
| 8 | 7 | α–C 10H 7 | 62 | 44 | S |
| 9 | 7 | β–C 10H 7 | >100 | 85 | S |
| 10 | 7 | 25 | 78 | R | |
| 11 | 7 | >100 | 87 | S |
The recycling of the recovery of table 2 part
| Cycle index | Part | Consumption/% | Reaction times/h | Productive rate/% | Ee value/% | Absolute configuration |
| 1 | 7 | 3 | 48 | 88 | 92 | S |
| 2 | 7 | 3 | 48 | 58 | 86 | S |
| 3 | 7 | 3 | 48 | 13 | 82 | S |
The chiral ferrocene methylene radical azepine little ring amino alcohol ligands of polyoxyethylene glycol load of the present invention obtains very high productive rate and stereoselectivity in the ethylation reaction of catalysis aromatic aldehyde, and the raw material of reaction is cheaply easy to get, the chiral ligand of synthesis is easy to modify, the method of part synthesis is simple, and the part of gained can be recycled, though reduce active, after recycling three times, selectivity product is relatively good.
Embodiment
The little ring amino alcohol ligands of chiral ferrocene methylene radical azepine of polyoxyethylene glycol load, it is connected with ehter bond by condensation reaction with the ferrocenyl azepine little ring ammonia alcohol part with graft site by methylsulfonyl poly glycol monomethyl ether, and structural formula is:
The synthetic method of the little ring amino alcohol ligands of chiral ferrocene methylene radical azepine of described polyoxyethylene glycol load:
(1) ferrocene methylene radical aziridinyl methyl-formiate and grignard reagent react, under the condition of 0-10 DEG C, the reaction times is 40-60 h, and described ferrocene methylene radical aziridinyl methyl-formiate is 1:2-8 with the ratio of the amount of substance of Grignard reagent, obtains
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol;
(2)
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol and TBAF react, and react 1-3 h under the condition of 10-30 DEG C, described in
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol are 1:2-4 with the ratio of the amount of substance of TBAF, and deprotection obtains
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol;
(3)
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid's base methyl alcohol and molecular weight be 2000 polyoxyethylene glycol react, under the condition of 60 ~ 70 DEG C, react 3-5h, described in
nthe ratio that-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol and molecular weight are the amount of substances of the polyoxyethylene glycol of 2000 is 1:1-3, obtains a kind of little ring amino alcohol ligands of chiral ferrocene methylene radical azepine of polyoxyethylene glycol load.
Compound
nthe synthesis of-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol 3:
0.5 g(22mmol is added in the round-bottomed flask of 50 mL) Mg bits, add the anhydrous THF of 8 mL again, add an iodine grain again, again 5.7 g(20 mmol) be dissolved in the anhydrous THF solution of 20 mL to tertiary butyl dimethyl Si base bromobenzene, be added dropwise in reaction flask, reflux 2 h, after reacting completely, be chilled to room temperature, then add 0.5 g(1.63 mmol)
n-ferrocenylmethyl aziridinyl methyl-formiate 2, uses TLC tracing detection, after reaction terminates, uses saturated ammonium chloride termination reaction.By extracted with diethyl ether, then carry out washing once with saturated sodium-chlor, with anhydrous sodium sulfate drying 2 h, pressure reducing and steaming ether, then use column chromatography purification (developping agent: V
ethyl acetate: V
sherwood oil=1/6) product 0.98 g (87%), is obtained.
1H NMR (400 MHz, CDCl
3) δ 7.24 – 7.13 (m, 4H,), 6.78 – 6.70 (m, 4H,), 4.12 – 4.03 (m, 9H,), 3.71 (s, 1H,), 3.51 (d,
J= 13.0 Hz, 1H,), 3.22 (d,
J= 13.0 Hz, 1H,), 2.31 (dd,
J= 6.3, 3.5 Hz, 1H,), 1.90 (d,
J= 3.5 Hz, 1H,), 1.48 (d,
J= 6.3 Hz, 1H,), 0.99 (s, 9H,), 0.96 (s, 9H,), 0.20 (d,
J= 0.7 Hz, 6H,), 0.18 (d,
J= 3.3 Hz, 6H).
IR (KBr) 3427, 3091, 2938, 2857, 1606, 1507, 1465, 1403, 1259, 1168, 916, 835, 672, 489.
HRMS(ESI): calcd for C
38H
53FeNO
3Si
2 [M]+ 683.2913, found 683.2944 [M+H]+ 684.2947, found 684.2990
Compound
nthe synthesis of-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol 4:
At-5 DEG C, add 1.61 mL TBAF (1 M in THF) in 50 mL single necked round bottom flask, 0.55 g (0.8 mmol) 3 is dissolved in the anhydrous THF of 5 mL, under agitation, slowly instills in reaction flask with constant pressure funnel.Drip and finish, then react 3 h, TLC tracing detection, after complete reaction, add 100 mL saturated sodium-chlorides, by extracted with diethyl ether to colourless, merge organic phase, anhydrous Na
2sO
4dry.Pressure reducing and steaming ether, puts into refrigerator and cooled but 2 h, filters, and institute's solid dry method loading is carried out column chromatography for separation purification (developping agent: V
methyl alcohol: V
methylene dichloride=1:20), obtain product 0.34 g (92%).
1H NMR (400 MHz, DMSO) δ 7.12 (dd,
J= 25.7, 8.6 Hz, 4H), 6.62 (dd,
J= 8.6, 1.9 Hz, 4H), 5.76 (s, 2H), 4.38 (s, 1H), 4.20 – 4.00 (m, 9H), 3.56 (d,
J= 13.0 Hz, 1H), 3.00 (d,
J= 13.0 Hz, 1H), 2.36 (dd,
J= 6.1, 3.3 Hz, 1H), 1.52 (d,
J= 3.0 Hz, 1H), 1.33 (d,
J= 6.2 Hz, 1H).
IR (KBr) 3389, 2925, 1603, 1510, 1447, 1367, 1169, 995, 828, 586, 488.
HRMS(ESI): calcd for C
26H
25FeNO
3 [M+H]+ 456.1262, found 456.1258
The synthesis of the little ring amino alcohol ligands 5 of chiral ferrocene methylene radical azepine of compound polyoxyethylene glycol load
In single neck round-bottomed flask of 25 mL, add 0.73 g(0.352mmol) methylsulfonyl poly glycol monomethyl ether (first in 50 DEG C of vacuum drying ovens dry 4 h); the Cs of 0.08 g (0.176 mmol) compound 4,0.229 g (0.737 mmol)
2cO
3, adding 3 mL dry DMF.Controlling temperature of reaction is 65 DEG C, thin-layer chromatography tracing detection, approximately reaction 4 h, and reaction terminates.Be cooled to 0 DEG C, slowly drip about 4 mL H
2o, 0.4mL (2M) HCl, then uses CH
2cl
2washing, merges CH
2cl
2phase, washs with saturated NaCl, uses anhydrous Na
2sO
4dry 2 h, then vacuum rotary steam, being stop to also remaining about 2 mL solvents, at putting into 0 DEG C, stirring, adding cold ether and precipitate, stir about 0.5 h, filter, obtain yellow solid 0.55 g, productive rate 98%.
1H NMR (400 MHz, CDCl
3) δ 7.24 (dd,
J= 19.8, 4H), 6.81 (t,
J= 8.7 Hz, 4H), 4.15 – 4.00 (m, 13H), 3.89 – 3.78 (m, 7H), 3.65 (s, 339H), 3.58 – 3.52 (m, 6H), 3.52 – 3.44 (m, 3H), 3.38 (s, 6H), 3.24 (d,
J= 13.1 Hz, 1H), 2.44 (s, 3H), 2.32 (s, 1H2), 1.88 (s, 1H), 1.48 (d,
J= 6.1 Hz, 1H).
IR (KBr) 2888, 1467, 1351, 1283, 1447, 1243, 1112, 955, 841, 525 .
The addition of zinc ethyl and phenyl aldehyde
Under 0 DEG C of condition, under nitrogen protection, with the anhydrous PhCH of 1.1mL
3for solvent, then add the chiral ligand of 3 mol%, add magneton and stir, slowly add the ZnEt of 1.1mL/M
2(being dissolved in normal hexane).Stir 30 min, now add the aldehyde of 0.5 mmol fast.Reaction mixture is at 0 DEG C, and continue stirring 10 h, rise to 25 DEG C, stir 38 h, with thin-layer chromatography tracing detection, it reacts completely, and uses NH
4cl termination reaction, Et
2oH extracts, and merges Et
2oH phase, washs once with saturated NaCl, anhydrous Na
2sO
4drying, Et is extracted in decompression
2oH, carries out purifying (V with thin-layer chromatography
ethyl acetate/ V
sherwood oil=1:6).
The preparation of racemic modification
Standby by conventional Grignard reagent legal system.In the there-necked flask of 25 mL dryings, add metal magnesium chips (50 mmol), slowly drip monobromethane (50 mmol are dissolved in 5 mL THF in advance), stir.After magnesium chips disappears, phenyl aldehyde (10 mmol are dripped under using ice bath instead, in 5 mL THF), after 20 minutes, use dilute hydrochloric acid acidifying, ether 10 mL × 3 extract, after merging organic phase, saturated common salt water washing, anhydrous sodium sulfate drying, column chromatography for separation (ethyl acetate: sherwood oil=1:6), obtains colourless liquid.
Claims (1)
1. a synthetic method for the little ring amino alcohol ligands of chiral ferrocene methylene radical azepine of polyoxyethylene glycol load, is characterized in that its step is as follows:
(1) compound
nthe synthesis of-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol:
In the round-bottomed flask of 50 mL, add 0.5 g Mg consider to be worth doing, add the anhydrous THF of 8 mL again, add an iodine grain again, again 5.7 g are dissolved in the anhydrous THF solution of 20 mL to tertiary butyl dimethyl Si base bromobenzene, be added dropwise in reaction flask, reflux 2 h, after reacting completely, be chilled to room temperature, then add 0.5 g's
n-ferrocenylmethyl aziridinyl methyl-formiate, uses TLC tracing detection, after reaction terminates, uses saturated ammonium chloride termination reaction, by extracted with diethyl ether, then carry out washing once with saturated sodium-chlor, with anhydrous sodium sulfate drying 2 h, pressure reducing and steaming ether, then use column chromatography purification, obtain 0.98g
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol;
(2) compound
nthe synthesis of-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol:
At-5 DEG C, add 1.61 mL TBAF in 50 mL single necked round bottom flask, 0.55 g
n-ferrocene methylene radical aziridinyl two pairs of tertiary butyl dimethyl Si base phenyl methanol are dissolved in the anhydrous THF of 5 mL, under agitation, slowly instill in reaction flask with constant pressure funnel; Drip and finish, then react 3 h, TLC tracing detection, after complete reaction, add 100 mL saturated sodium-chlorides, by extracted with diethyl ether to colourless, merge organic phase, anhydrous Na
2sO
4drying, pressure reducing and steaming ether, puts into refrigerator and cooled but 2 h, suction filtration, gained solid dry method loading is carried out column chromatography for separation purification, obtains 0.34g
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol;
(3) synthesis of the little ring amino alcohol ligands of chiral ferrocene methylene radical azepine of compound polyoxyethylene glycol load
The methylsulfonyl poly glycol monomethyl ether of 0.73 g is added in single neck round-bottomed flask of 25 mL, 0.08 g's
n-ferrocene methylene radical aziridinyl two Pyrogentisinic Acid base methyl alcohol, the Cs of 0.229 g
2cO
3, then add 3 mL dry DMF, controlling temperature of reaction is 65 DEG C, and thin-layer chromatography tracing detection, reacts 4 h, and reaction terminates, and is cooled to 0 DEG C, slowly drips 4 mL H
2o, 0.4mL concentration is the HCl of 2M, then uses CH
2cl
2washing, merges CH
2cl
2phase, washs with saturated NaCl, uses anhydrous Na
2sO
4dry 2 h, then vacuum rotary steam, stop to when also remaining 2 mL solvent, at putting into 0 DEG C, stirs, add cold ether and precipitate, stir 0.5 h, suction filtration, obtain 0.55g yellow solid.
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