CN104610003B - A kind of method of high-efficient carrier catalyst asymmetry catalysis Michael addition - Google Patents
A kind of method of high-efficient carrier catalyst asymmetry catalysis Michael addition Download PDFInfo
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- nitroolefin
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- KXIKKCAQRYXRMY-VXGBXAGGSA-N C[n]1c(S(N[C@H](CCCC2)[C@@H]2N)(=O)=O)[n+](CCC[SiH3])cc1 Chemical compound C[n]1c(S(N[C@H](CCCC2)[C@@H]2N)(=O)=O)[n+](CCC[SiH3])cc1 KXIKKCAQRYXRMY-VXGBXAGGSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of chirality supported catalyst efficient, eco-friendly, do with water and under solvent room temperature reaction condition, realize isobutylaldehyde and nitroolefin asymmetric Michael reaction method.The little molecule of chirality that described method includes modifying with superparamagnetic nanoparticle load, " ion atmosphere " is for catalyst, N, N-lutidines (DMAP) is accelerator, 25 DEG C, isobutylaldehyde carries out stereo selectivity Michael additive reaction with nitroolefin under normal pressure, supported catalyst is reused 5 times, does not find that reaction yield and ee value are decreased obviously.This method is simple to operate, catalyst stereo selectivity is good, it is simple to reclaim, catalystic converter system reusability is good, reaction condition is gentle, it is easy to accomplish large-scale production.
Description
Technical field
The present invention relates to a kind of efficient, green, do under solvent condition with water, with novel superparamagnetic nano load, ion atmosphere " the little molecule of chirality modified is for catalyst; N, N-lutidines (DMAP) is accelerator, 25 DEG C, isobutylaldehyde carries out asymmetric Michael addition reaction method with nitroolefin under normal pressure.
Technical background
Nitroparaffins because easily carrying out alpha-alkyl reaction and be converted into other important functional group, have in organic synthesis important function (CzekeliusC, CarreiraEM.Angew.Chem.Int.Ed., 2005,44,612；BernerOM,TedeschiL,EndersD.Eur.J.Org.Chem.,2002,2002,1877.).The conjugate addition of the nucleopilic reagent centered by carbon and nitroolefin is the method for most common preparation chiral nitro alkane.Wherein, most importantly utilize carbonyl compound and nitroolefin Michael additive reaction (BetancortJM, BarbasCF, Org.Lett., 2001,3,3737；MelchiorreP,KA,J.Org.Chem.,2003,68,4151；AustinJF,MacMillanDWC,J.Am.Chem.Soc.,2002,124,1172；DavieEAC,MennenSM,XuY,etal.Chem.Rev.,2007,107,5759.).
In recent years, asymmetric organocatalysis causes chemists and pays close attention to widely, has emerged a series of proline salt, chiral metal complex catalyst etc., the aldehyde asymmetric conjugated reaction with nitroolefin achieves certain effect (LiH, WangY, TangL, WuF, LiuX, GuoC, FoxmanBM, DengL, Angew.Chem.Int.Ed., 2005,44,105；MalerichJP,HagiharaK,RawalVH,J.Am.Chem.Soc.,2008,130,14416；YuZ,LiuX,ZhouL,LinL,FengX,Angew.Chem.Int.Ed.,2009,48,5195.).But said method also exists a large amount of poisonous and harmful solvents of use, uses the defects such as catalyst recovery difficulty.Therefore, catalysis activity is good, reclaim simple novel load catalyst to be highly desirable to develop solid.
With conventional load polymer phase ratio, superparamagnetic nanoparticle not only size is in nanoscale, it is ensured that catalytic reaction, and is easily separated by externally-applied magnetic field, better solves separation and the recovery of catalyst.Therefore in recent years, superparamagnetic nanoparticle supported catalyst have become as people explore eco-friendly catalystic converter system important directions (GawandeMB, BrancoPS, VarmaSV, Chem.Soc.Rev., 2013,42,3371；BaigRBN,VarmaS,Chem.Commun.,2013,49,752).Ionic liquid has the feature such as thermodynamic stability, solvability strong, low volatility, molecular structure adjustability.We are in conjunction with the advantage of superparamagnetic nanoparticle Yu both ionic liquids, design superparamagnetic nanoparticle load, catalyst that " ion atmosphere " is modified be successfully applied in organic synthesis, achieve good effect (Ying, A, LiuS, NiY, QiuF, XuS, TangW, Catal.Sci.Technol., 2014,4,2115；YingA,QiuF,WuC,HuH,YangJ.,RSCAdv.,2014,4,33173.).It is therefore desirable to the chiral catalyst that exploitation superparamagnetic nano load, " ion atmosphere " are modified is in asymmetric Michael addition reaction.
Summary of the invention
It is an object of the invention to replace traditional asymmetry catalysis isobutylaldehyde and nitroolefin Michael addition method, it is provided that a kind of loaded chiral catalyst efficient, eco-friendly, do with water and realize Michael addition under solvent gentleness (room temperature) reaction condition.
According to the present invention, the described method carrying out stereo selectivity Michael addition by isobutylaldehyde and nitroolefin, it is characterized in that, described method includes with superparamagnetic nanoparticle load, the little molecule of chirality that " ion atmosphere " is modified is catalyst, room temperature (25 DEG C), under normal pressure, isobutylaldehyde and nitroolefin carry out asymmetric Michael addition reaction, including: with superparamagnetic nanoparticle load, " ion atmosphere " modifies the little molecule of chirality is catalyst, room temperature (25 DEG C), under normal pressure, solvent is made with water, isobutylaldehyde and nitroolefin carry out asymmetric Michael addition reaction 1～10 hour, obtain corresponding chiral nitro substituent.Wherein, described catalyst is:
Wherein, described isobutylaldehyde is 1:1-10:1 with the mol ratio of nitroolefin.
Wherein, the mole of described catalyst is 0.1-1 times of nitroolefin.
Wherein, 0.01-0.5 times that mole is nitroolefin of described additive DMAP.
Wherein, described nitroolefin material is (I) formula structure, wherein Ar includes benzene, 4-Nitrobenzol, 3-Nitrobenzol, 2-chlorobenzene, 4-chlorobenzene, 4-methoxybenzene, 4-hydroxy benzenes, 3,4-dimethoxy benzenes, 3-methoxyl group-4-hydroxy benzenes, 1-naphthyl and 2-thiophene.
Wherein, described reaction medium is water.
Wherein, after reaction terminates, being extracted with ethyl acetate reactant liquor, merge organic facies, column chromatography for separation obtains product.Catalyst can be reclaimed by externally-applied magnetic field, after ethyl acetate washing, for applying mechanically next time after 60 DEG C of vacuum dryings 5 hours.
The little molecular stereo selective catalysis isobutylaldehyde of the chirality utilizing New Magnetic Field Controlled nano-particle load, " ion atmosphere " to modify provided by the invention and the addition method of the Michael of nitroolefin, realized by following approach:
The preparation process of new function ionic liquid used in the present invention:
Take 1g1, add 50mL dry toluene, ultrasonic 1h.Add 3-chloropropyl triethoxysilane (4g, 4mL), mechanical agitation backflow 24h at nitrogen protection 110 DEG C.Reactant liquor is cooled to room temperature, and brown solid 2 magnet obtained is collected, with alcohol flushing, 60 DEG C of vacuum drying 10h.Take 0.3g3, add 0.358g3, add 20mL dry toluene, ultrasonic 1h, mechanical agitation backflow 48h at nitrogen protection 110 DEG C.Reactant liquor is cooled to room temperature, and brown solid 4 magnet obtained is collected, with alcohol flushing, 60 DEG C of vacuum drying 10h.Adding 10mL dichloromethane, 1mL trifluoroacetic acid by 4,10h is stirred at room temperature, remove solvent, saturated NaHCO used successively by remaining solid3Solution, water, washed with methanol, 60 DEG C of vacuum drying 10h obtain final catalyst.Through elementary analysis, the payload amount of catalyst is 0.882mmol/g.
Asymmetric Michael reaction product preparation process is:
Equipped with, in the there-necked flask of magnetic stirring apparatus, being sequentially added into isobutylaldehyde, nitroolefin, DMAP and catalyst.Wherein isobutylaldehyde is 1:1-10:1 with the mol ratio of nitroolefin, the mole of catalyst is 0.1-1 times of nitroolefin, the mole of additive DMAP is 0.01-0.5 times of nitroolefin, doing solvent, 25 DEG C, synthesis under normal pressure 1-10 hour with water, thin layer chromatography (TLC) follows the tracks of extent of reaction.After reaction terminates, it is extracted with ethyl acetate reactant liquor, merges organic facies, column chromatography for separation obtains product, and raffinate phase applied magnet reclaims catalyst, and ethyl acetate is washed, 60 DEG C of vacuum dryings reacted for next batch after 5 hours, and catalyst is reused 5 times, does not find that reaction yield is decreased obviously.
Detailed description of the invention
Below with reference to embodiment, the present invention will be further described, and embodiments of the invention are merely to illustrate technical scheme the non-limiting present invention.
Embodiment 1
Take nitrostyrolene (0.2mmol, 29.8mg), isobutylaldehyde (1mmol, 0.91mL), in 5mL flask, adds catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 4h under room temperature, reaction process goes TLC to detect.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1).Product passes through1HNMR and HPLC analyzes, yield 87%.
(R)-2,2-Dimethyl-4-nitro-3-phenylbutanal:Theeewasdeterminedb yHPLCwithChiralpakOD-Hcolumnat210nm (hexane/i-PrOH=80:20, flowrate0.5mL/min, 20 DEG C) .tR(major)=31.8min, tR(minor)=38.5min, ee=97%.1HNMR(400MHz,CDCl3):δ9.55(s,1H),7.31-7.37(m,3H),7.21-7.23(m,2H),4.85-4.91(m,1H),4.69-4.74(m,1H),3.79-3.83(m,1H),1.15(s,3H),1.02(s,3H).
Embodiment 2
Take nitrostyrolene (0.2mmol, 29.8mg), isobutylaldehyde (1mmol, 0.91mL), in 5mL flask, adds catalyst (0.03mmol, 23mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 7h under room temperature, reaction process goes TLC to detect.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1).Product passes through1HNMR and HPLC analyzes, yield 83%, ee=97%.
Embodiment 3
Take nitrostyrolene (0.2mmol, 29.8mg), isobutylaldehyde (2mmol, 0.91mL), in 5mL flask, adds catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 4h under room temperature, reaction process goes TLC to detect.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1).Product passes through1HNMR and HPLC analyzes, yield 86%, ee=98%.
Embodiment 4
Take 4-nitro-beta-nitrostyrene (0.2mmol, 38.8mg), isobutylaldehyde (1mmol, 0.91mL) in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 4h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1), yield 91%.
(R)-2,2-dimethyl-4-nitro-3-(4-nitrophenyl) butanal:TheeewasdeterminedbyHPLCwithChiralpakOD-Hcolumna t208nm (hexane/i-PrOH=75:25, flowrate0.5mL/min, 20 DEG C) .tR(major)=10.6min, tR(minor)=11.6min, ee=99%.1HNMR(400MHz,CDCl3): δ 9.51 (s, 1H), 8.22 (d, 2H, J=8.8Hz), 7.45 (d, 2H, J=8.8Hz), 4.91-4.97 (m, 1H), 4.77-4.82 (m, 1H), 3.93-3.97 (m, 1H), 1.18 (s, 3H), 1.07 (s, 3H).
Embodiment 5
Take 3-nitro-beta-nitrostyrene (0.2mmol, 38.8mg), isobutylaldehyde (1mmol, 0.91mL) in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic stirring apparatus 3h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1), yield 92%.
(R)-2,2-dimethyl-4-nitro-3-(3-nitrophenyl) butanal:TheeewasdeterminedbyHPLCwithChiralpakOD-Hcolumna t254nm (hexane/i-PrOH=90:10, flowrate0.2mL/min, 20 DEG C) .tR(major)=30.5min, tR(minor)=31.7min, ee=99.8%.1HNMR(400MHz,CDCl3):δ9.52(s,1H),8.22(t,1H),8.15(t,1H),7.55-7.62(m,2H), 4.92-4.98(m,1H),4.78-4.82(m,1H),3.95-3.98(m,1H),1.10(s,3H),1.08(s,3H).
Embodiment 6
(R)-2, the preparation of 2-dimethyl-4-nitro-3-(2-chlorphenyl) butyraldehyde: take the chloro-beta-nitrostyrene (0.2mmol of 2-, 36.7mg), isobutylaldehyde (1mmol, 0.91mL) is in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 5h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=10:1), yield 89%.
(R)-2,2-dimethyl-4-nitro-3-(2-chlorophenyl) butanal:TheeewasdeterminedbyHPLCwithChiralpakOD-Hcolumna t254nm (hexane/i-PrOH=90:10, flowrate0.2mL/min, 20 DEG C) .tR(major)=19.3min, tR(minor)=20.8min, ee=97%.1HNMR(400MHz,CDCl3): δ 9.57 (s, 1H), 7.44 (d, 1H, J=7.6Hz), 7.27-7.31 (m, 2H), 7.23-7.26 (m, 1H), 4.86 (t, 1H), 4.72-4.83 (m, 1H), 4.63-4.67 (m, 1H), 1.18 (s, 3H), 1.09 (s, 3H).
Embodiment 7
Take 4-methoxyl group-beta-nitrostyrene (0.2mmol, 35.8mg), isobutylaldehyde (1mmol, 0.91mL) in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 4h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=10:1), yield 81%.
(R)-3-(4-methoxyphenyl)-2,2-dimethyl-4-nitrobutanal:TheeewasdeterminedbyHPLCwithCh iralpakOD-Hcolumnat210nm (hexane/i-PrOH=75:25, flowrate0.5mL/min, 20 DEG C) .tR(major)=13.2min, tR(minor)=14.9min, ee=97%.1HNMR(400MHz,CDCl3): δ 9.54 (s, 1H), 7.13 (d, 2H, J=8.4Hz), 6.87 (d, 2H, J=8.4Hz), 4.79-4.85 (m, 1H), 4.66-4.70 (m, 1H), 3.80 (s, 3H), 3.73-3.77 (m, 1H), 1.14 (s, 3H), 1.02 (s, 3H).
Embodiment 8
Disubstituted-4-hydroxy-beta-nitrostyrene (0.2mmol, 33.0mg), isobutylaldehyde (1mmol, 0.91mL) in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 3h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1), yield 85%.
(R)-3-(4-hydroxyphenyl)-2,2-dimethyl-4-nitrobutanal:(Table8, entry7) .TheeewasdeterminedbyHPLCwithChiralpakOD-Hcolumnat254nm (hexane/i-PrOH=90:10, flowrate0.2mL/min, 20 DEG C) .tR(major)=50.1min, tR(minor)=56.7min, ee=95%.1HNMR(400MHz,CDCl3): δ 9.51 (s, 1H), 7.04 (d, 2H, J=7.6Hz), 6.54 (s, 1H), 4.82 (t, 1H), 4.65-4.69 (m, 1H), 3.71-3.75 (m, 1H), 1.11 (s, 3H), 0.99 (s, 3H).
Embodiment 9
Take 3,4-dimethoxy-beta-nitrostyrene (0.2mmol, 41.8mg), isobutylaldehyde (1mmol, 0.91mL) is in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 5h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=3:1), yield 83%.
(R)-3-(3,4-dimethoxyphenyl)-2,2-dimethyl-4-nitrobutanal:TheeewasdeterminedbyHPLCwithCh iralpakOD-Hcolumnat254nm (hexane/i-PrOH=90:10, flowrate0.2mL/min, 20 DEG C) .tR(major)=34.2min, tR(minor)=36.0min, ee=96%.1HNMR(400MHz,CDCl3): δ 9.54 (s, 1H), 6.83 (d, 1H, J=8.4Hz), 6.75-6.78 (m, 1H), 6.69 (s, 1H), 4.82-4.88 (m, 1H), 4.67-4.71 (m, 1H), 3.89 (s, 3H), 3.88 (s, 3H), 3.71-3.75 (m, 1H), 1.16 (s, 3H), 1.05 (s, 3H).
Embodiment 10
Take 1-(2-nitroethylene base) naphthalene (0.2mmol, 39.8mg), isobutylaldehyde (1mmol, 0.91mL) in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 6h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1), yield 84%.
(R)-2,2-dimethyl-3-(naphthalen-1-yl)-4-nitrobutanal:TheeewasdeterminedbyHPLCwithChiralpakOD-H columnat254nm (hexane/i-PrOH=90:10, flowrate0.2mL/min, 20 DEG C) .tR(major)=31.6min, tR(minor)=35.5min, ee=96%.1HNMR(400MHz,CDCl3): δ 9.61 (s, 1H), 8.25 (d, 1H, J=8.8Hz), 8.88 (d, 1H, J=7.6Hz), 7.83 (d, 1H, J=8.0Hz), 7.61-7.63 (m, 1H), 7.43-7.59 (m, 3H), 4.96-5.05 (m, 2H), 4.87-4.90 (m, 1H), 1.23 (s, 3H), 0.98 (s, 3H).
Embodiment 11
Take 2-nitrothiophene ethylene (0.2mmol, 31.0mg), isobutylaldehyde (1mmol, 0.91mL) in 5mL flask, add catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 5h under room temperature.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=10:1), yield 86%.
(R)-2,2-dimethyl-4-nitro-3-(thiophen-2-yl) butanal:TheeewasdeterminedbyHPLCwithChiralpakOD-Hcolumna t254nm (hexane/i-PrOH=90:10, flowrate0.2mL/min, 20 DEG C) .tR(major)=36.7min, tR(minor)=40.7min, ee=99.6%.1HNMR (400MHz,CDCl3): δ 9.56 (s, 1H), 7.27 (d, 1H, J=4.8Hz), 6.94-6.99 (m, 2H), 4.66-4.78 (m, 2H), 4.14-4.18 (m, 1H), 1.23 (s, 3H), 1.10 (s, 3H).
Embodiment 12
Take nitrostyrolene (0.2mmol, 29.8mg), isobutylaldehyde (1mmol, 0.91mL), in 5mL flask, adds catalyst (0.03mmol, 34mg), DMAP (0.04mmol, 4.9mg), water (1mL), magnetic agitation 4h under room temperature, reaction process goes TLC to detect.After having reacted, being extracted with ethyl acetate for several times, merge organic facies, wet method crosses post (eluant: petroleum ether: ethyl acetate=5:1).Product passes through1HNMR and HPLC analyzes, yield 87%.
Ionic liquid is reused 5 times, does not find that yield is decreased obviously, and is specifically shown in table 1.NMR DATA Example 1.
Table 1
It should be noted that foregoing invention content and detailed description of the invention are intended to prove the practical application of technical scheme provided by the present invention to should not be construed as limiting the scope of the present invention.Those skilled in the art are in the spirit and principle of the present invention, when doing various amendment, equivalent replacement or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (8)
1. the method carrying out stereo selectivity Michael addition by isobutylaldehyde and nitroolefin, it is characterized in that, described method includes with the little molecule of chirality of superparamagnetic nanoparticle load for catalyst, DMAP is additive, 25 DEG C, isobutylaldehyde and nitroolefin carry out asymmetric Michael addition reaction under normal pressure；Wherein, described nitroolefin is formula (I) structure:
Wherein Ar is benzene, 4-Nitrobenzol, 3-Nitrobenzol, 2-chlorobenzene, 4-chlorobenzene, 4-methoxybenzene, 4-hydroxy benzenes, 3,4-dimethoxy benzene, 3-methoxyl group-4-hydroxy benzenes, 1-naphthyl and 2-thiophene；Described catalyst is:
2. the method for claim 1, it is characterised in that the mol ratio of described isobutylaldehyde and nitroolefin is 1:1-10:1.
3. the method for claim 1, it is characterised in that the mole of described catalyst is 0.1-1 times of nitroolefin.
4. the method for claim 1, it is characterised in that 0.01-0.5 times that mole is nitroolefin of described additive DMAP.
5. the method for claim 1, it is characterised in that course of reaction makees solvent with water.
6. the method as described in claim 1 or 5, it is characterised in that the response time is 1～10 hour.
7. method as claimed in claim 6, it is characterised in that after reaction terminates, being extracted with ethyl acetate reactant liquor, merge organic facies, column chromatography for separation obtains product.
8. method as claimed in claim 7, it is characterised in that after reaction terminates, catalyst is reclaimed by externally-applied magnetic field, after ethyl acetate washing, for applying mechanically next time after 60 DEG C of vacuum dryings 5 hours.
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| CN102441431A (en) * | 2011-09-30 | 2012-05-09 | 中国科学院长春应用化学研究所 | Catalyst for Michael addition reaction and preparation method of nitro fatty aldehyde |
| CN102942430A (en) * | 2012-12-03 | 2013-02-27 | 中国科学技术大学 | Preparation method of addition product of aldehyde and nitroolefin |
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| CN102441431A (en) * | 2011-09-30 | 2012-05-09 | 中国科学院长春应用化学研究所 | Catalyst for Michael addition reaction and preparation method of nitro fatty aldehyde |
| CN102942430A (en) * | 2012-12-03 | 2013-02-27 | 中国科学技术大学 | Preparation method of addition product of aldehyde and nitroolefin |
Non-Patent Citations (2)
| Title |
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| Functionalization of Fe3O4 magnetic nanoparticles for organocatalytic Michael reactions;Paola Riente et al.;《Journal of Materials Chemistry》;20110408;第21卷;第7350-7355 * |
| Hybrid magnetic materials (Fe3O4ek-carrageenan) as catalysts for the Michael addition of aldehydes to nitroalkenes;Carmen A. Mak et al.;《Tetrahedron》;20140620;第70卷;第6169-6173页 * |
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