CN105985279A - Method for preparing indole derivative by reaction between nitrone derivative and symmetric alkyne - Google Patents
Method for preparing indole derivative by reaction between nitrone derivative and symmetric alkyne Download PDFInfo
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- CN105985279A CN105985279A CN201510058946.8A CN201510058946A CN105985279A CN 105985279 A CN105985279 A CN 105985279A CN 201510058946 A CN201510058946 A CN 201510058946A CN 105985279 A CN105985279 A CN 105985279A
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Abstract
The invention relates to a method for preparing an indole derivative by a reaction between a nitrone derivative and symmetric alkyne and particularly relates to a novel method for preparing a 2,3-asymmetric indole derivative by a reaction between a nitrone compound and the symmetric alkyne under the catalysis of trivalent rhodium. According to the method, a transition metal catalyst is used, the 2,3-asymmetric indole derivative is obtained through simple operating steps, and the reaction is good in selectivity and relatively high in yield.
Description
Technical field
The present invention relates to one under transition metal rhodium catalysis by nitrone analog derivative and symmetrical alkynes
Hydrocarbon reaction prepares the method for indole derivatives.
Background technology
Indoles is one of most important heterocycle, is widely present in natural products, medicine and function material
(document 1:(a) Sundberg in material, R.J.Indoles, Academic Press, San Diego,
1996.(b)Eicher,T.；Hauptmann,S.The Chemistry of Heterocycles:
Structure,Reactions,Syntheses,and Applications,2nd ed.,Wiley-VCH,
Weinheim,2003.(c)Somei,M.；Yamada,F.Nat.Prod.Rep.2004,21,
278.(d)Kawasaki,T.；Higuchi,K.Nat.Prod.Rep.2005,22,761.(e)
Somei,M.；Yamada,F.Nat.Prod.Rep.2005,22,73.(f)
Kochanowska-Karamyan,A.J.；Hamann,M.T.Chem.Rev.2010,110,
4489.).Being carried out the method for indole synthesis by metal catalytic has a three class method: method one:
Prepare (document 2:(a) Kraus, G.A. by classical nucleophilic addition；Guo,H.J.Org.
Chem.2009,74,5337.(b)Kim,T.；Kim,K.Tetrahedron Lett.2010,51,
868.) method two: transition metal-catalyzed cross-coupling reaction prepares (document 3:(a)
Nakamura,M.；Iiies,L.；Otsubo,S.；Nakamura,E.Org.Lett.2006,8,
2803.(b)Lu,B.Z.；Zhao,W.；Wei,H.X.；Dufour,M.；Farina,V.；
Senanayake,C.H.Org.Lett.2006,8,3271.(c)Shen,Z.；Lu,X.
Tetrahedron 2006,62,10896.(d)Cacchi,S.；Fabrizi,G.；Goggiamani,A.
Adv.Synth.Catal.2006,348,1301.(e)Isono,N.；Lautens,M.Org.Lett.
2009,11,1329.(f)Cacchi,S.；Fabrizi,G.；Goggiamani,A.；Perboni,A.；
Sferrazza,A.；Stabile,P.Org.Lett.2010,12,3279.(g)Shibata,T.；
Hirashima,H.；Kasagawa,M.；Tsuchikama,K.；Endo,K.Synlett 2011,15,
2171.(h)Yao,B.；Wang,Q.；Zhu,J.Angew.Chem.,Int.Ed.2012,51,
12311.(i)Lu,B.Z.；Wei,H.W.；Zhang,Y.；Zhao,W.；Dufour,M.；Li,G.；
Farina,V.；Senanayake,C.H.J.Org.Chem.2013,78,4558.(j)
Breazzano,S.P.；Poudel,Y.B.；Boger,D.L.J.Am.Chem.Soc.2013,135,
1600.) method three: build nitrogenous guiding group, close through the C-H activation of transition metal
Become indoles (document 3:(a) Shen, M.；Li,G.；Lu,B.Z.；Hossain,A.；Roschangar,
F.；Farina,V.；Senanayake,C.H.Org.Lett.2004,6,4129.(b)Stuart,D.
R.；Bertrand-Laperle,M.；Burgess,K.M.；Fagnou,K.J.Am.Chem.Soc.
2008,130,16474.(c)Shi,Z.；Zhang,C.；Li,S.；Pan,D.；Ding,S.；Cui,Y.；
Jiao,N.Angew.Chem.,Int.Ed.2009,48,4572.(d)Stuart,D.R.；Alsabeh,
P.；Kuhn,M.；Fagnou,K.J.Am.Chem.Soc.2010,132,18326.(e)Chen,
J.；Song,G.；Pan,C.L.；Li,X.Org.Lett.2010,12,5426.(f)Huestis,M.
P.；Chan,L.；Stuart,D.R.；Fagnou,K.Angew.Chem.,Int.Ed.2011,50,
1338.(g)Chen,J.；Pang,Q.；Sun,Y.；Li,X.J.Org.Chem.2011,76,3523.
(h)Wang,H.；Grohmann,C.；Nimphius,C.；Glorius,F.J.Am.Chem.Soc.
2012,134,19592.(h)Ackermann,L.；Lygin,A.V.Org.Lett.2012,14,
764.) we have developed and have been reacted with symmetrical alkynes through nitrone analog derivative by transition metal rhodium catalysis
Prepare the new method of indole derivatives.The method can optionally synthesize 2,3 through a step
The indole derivatives of different substituents, yield is high, and simple to operate and cheaper starting materials is easy to get.
Content of the invention
It is an object of the invention to provide a kind of method of synthesis of indole derivative, nitrone class derives
Thing and symmetrical alkynes are raw material generation 2, the asymmetric indole derivatives of 3-, and reaction equation is as follows:
Described metallic catalyst is the metal precursor of trivalent rhodium, silver salt and mantoquita；
Substituent R in described reactant and product1For C1-C10 alkyl, aryl or halogen, virtue
Base is the aryl on phenyl or phenyl ring with substituent；R2For C1-C10 alkyl or containing miscellaneous former
The heteroaryl perfume base of sub-O or S, aryl or halogen, heteroaryl perfume base is thienyl or furyl,
Aryl is the aryl on phenyl or phenyl ring with substituent；R3For C4-C10 alkyl or containing miscellaneous
The heteroaryl perfume base of atom O or S, aryl, heteroaryl perfume base is thienyl or furyl, aryl
For the aryl with substituent on phenyl or phenyl ring.
Described solvent is oxolane, 1,4-dioxane, glycol dimethyl ether, ethylene glycol
Diethyl ether, 1,2-dichloroethanes, 1, one or two or more kinds in 3-dichloropropane, the use of solvent
Amount is every 0.25 mM of reactant (2) 14 milliliters.
Described reaction temperature is 60 120 DEG C；The described reaction time is 6-16 hour.
Described catalyst uses in-situ preparation method, under argon shield, before rhodium salt metal
Body and silver salt 1:4 in molar ratio, adds copper after stirring 20-30 minute in solvent at room temperature
Salt.
Described metal precursor is that dichloro (pentamethylcyclopentadiene base) closes rhodium (III) dimer
([RhCp*Cl2]2)；Silver salt is silver hexafluoroantimonate or silver trifluoromethanesulfonate；Mantoquita is anhydrous vinegar
Acid copper and/or acetic anhydride are cuprous；The rhodium metal precursor mole adding is symmetrical alkynes
2.5% to 5%, the mole dosage of silver salt is 10% to the 20% of symmetrical alkynes, mantoquita mole
Consumption is the 1-2 times amount of symmetrical alkynes.
The mole dosage of described nitrone analog derivative and symmetrical alkynes ratio is for 1.2:1.
Present invention have the advantage that
1. reactant nitrone is obtained through simple reaction step by raw material aldehyde cheap and easy to get, nitrobenzene
Arrive；Symmetrical alkynes is obtained through simple reaction step by Terminal Acetylenes, and raw material is simple and easy to get.
2. reaction lower obtain 2,3 different pair through a step just high yield transition metal-catalyzed and takes
For indole derivatives, simple to operate efficiently.
Brief description
Fig. 1 is compound 3a1H NMR spectra；
Fig. 2 is compound 3a13C NMR spectra；
Fig. 3 is compound 3b1H NMR spectra；
Fig. 4 is compound 3b13C NMR spectra；
Fig. 5 is compound 3c1H NMR spectra；
Fig. 6 is compound 3c13C NMR spectra；
Fig. 7 is compound 3d1H NMR spectra；
Fig. 8 is compound 3d13C NMR spectra.
Detailed description of the invention
In order to be more fully understood that the present invention, illustrated by following instance.
Embodiment 1
Reacting in reactor, reactor after after vacuumizing, logical argon gas replaces three times, adds
Rhodium salt metal precursor (0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6
Mg), dioxane 2 milliliters, after stirring 30 minutes, addition Salicylaldoxime (0.25mmol,
45.4mg), nitrone 1a (0.3mmol, 68.1mg) and symmetrical alkynes 2a (0.25mmol, 44.5
Mg), stirring reaction 16 hours at 100 DEG C.After reaction terminates, taken out molten by Rotary Evaporators
Agent, then column chromatography for separation, eluant, eluent is petroleum ether: the mixed solvent of ethyl acetate=20:1,
Obtain the indoles 3a of 60.5mg.Separation yield is 81%.
The sign data of compound 3a are as follows:
1H NMR(400MHz,CDCl3) 8.12 (s, 1H), 7.66 (d, J=7.9Hz, 1H),
7.43 (d, J=7.1Hz, 2H), 7.39 7.29 (m, 5H), 7.27 (t, J=7.3Hz, 1H),
7.20 (t, J=5.2Hz, 1H), 7.13 (t, J=7.8Hz, 1H), 6.83 (d, J=8.8Hz, 2H),
3.78(s,3H)；(spectrogram is shown in Figure of description 1)
13C NMR(100MHz,CDCl3)δ159.4,135.9,135.4,134.3,130.3,
129.6,129.0,128.6,126.2,125.3,122.5,120.5,119.6,114.3,110.9,55.4.
(spectrogram is shown in Figure of description 2)
Embodiment 2
Reacting in reactor, reactor after after vacuumizing, logical argon gas replaces three times, adds
Rhodium salt metal precursor (0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6
Mg), dioxane 2 milliliters, after stirring 30 minutes, addition Salicylaldoxime (0.25mmol,
45.4mg), nitrone 1b (0.3mmol, 72.3mg) and symmetrical alkynes 2a (0.25mmol, 44.5
Mg), stirring reaction 16 hours at 100 DEG C.After reaction terminates, taken out molten by Rotary Evaporators
Agent, then column chromatography for separation, eluant, eluent is petroleum ether: the mixed solvent of ethyl acetate=20:1,
Obtain the indoles 3b of 64.2mg.Separation yield is 82%.
The sign data of compound 3b are as follows:
1H NMR(400MHz,CDCl3) δ 8.01 (s, 1H), 7.42 (d, J=7.8Hz, 3H),
7.36 (t, J=7.5Hz, 2H), 7.33 7.23 (m, 4H), 7.03 (d, J=8.2Hz, 1H),
6.83 (d, J=8.4Hz, 2H), 3.78 (s, 3H), 2.42 (s, 3H)；(spectrogram is shown in Figure of description
3)
13C NMR(100MHz,CDCl3)δ159.3,135.6,134.4,134.3,130.3,
129.78,129.5,129.3,128.6,126.2,125.5,124.1,119.2,114.3,114.0,
(110.6,55.4,21.7. spectrogram is shown in Figure of description 4)
Embodiment 3
Reacting in reactor, reactor after after vacuumizing, logical argon gas replaces three times, adds
Rhodium salt metal precursor (0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6
Mg), dioxane 2 milliliters, after stirring 30 minutes, addition Salicylaldoxime (0.25mmol,
45.4mg), nitrone 1c (0.3mmol, 82.8mg) and symmetrical alkynes 2a (0.25mmol, 44.5
Mg), stirring reaction 16 hours at 100 DEG C.After reaction terminates, taken out molten by Rotary Evaporators
Agent, then column chromatography for separation, eluant, eluent is petroleum ether: the mixed solvent of ethyl acetate=20:1,
Obtain the indoles 3c of 56.6mg.Separation yield is 65%.
The sign data of compound 3c are as follows:
1H NMR(400MHz,CDCl3) δ 8.17 (s, 1H), 7.66 (d, J=8.0Hz, 1H),
7.40 (m, 7H), 7.32 7.22 (m, 4H), 7.15 (t, J=7.5Hz, 1H)；(spectrogram is shown in
Bright book accompanying drawing 5)
13C NMR(100MHz,CDCl3)δ136.1,134.3,132.9,132.0,131.8,
130.2,129.74,128.9,128.8,126.6,123.2,121.9,120.8,119.9,1 11.1. (spectrum
Figure is shown in Figure of description 6)
Embodiment 4
Reacting in reactor, reactor after after vacuumizing, logical argon gas replaces three times, adds
Rhodium salt metal precursor (0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6
Mg), dioxane 2 milliliters, after stirring 30 minutes, addition Salicylaldoxime (0.25mmol,
45.4mg), nitrone 1d (0.3mmol, 59.1mg) and symmetrical alkynes 2b (0.25mmol, 59.5
Mg), stirring reaction 16 hours at 100 DEG C.After reaction terminates, taken out molten by Rotary Evaporators
Agent, then column chromatography for separation, eluant, eluent is petroleum ether: the mixed solvent of ethyl acetate=20:1,
Obtain the indoles 3d of 60.5mg.Separation yield is 81%.
The sign data of compound 3d are as follows:
1H NMR (400MHz, CDCl3) δ 8.18 (s, 1H), 7.64 (d, J=7.7Hz, 1H),
7.42 (t, J=6.9Hz, 3H), 7.38 7.20 (m, 6H), 7.14 (s, 1H), 6.93 (d, J=8.6
Hz,2H),3.84(s,3H)；(spectrogram is shown in Figure of description 7)
13C NMR(100MHz,CDCl3)δ158.3,136.0,133.8,133.0,131.3,
129.1,128.8,128.2,127.7,127.5,122.8,120.5,119.8,114.9,114.2,
110.98,55.4；(spectrogram is shown in Figure of description 8)
From above example and each collection of illustrative plates, the method that the present invention provides is raw materials used simple easy
, reaction is to preparation 2, and the asymmetric indole derivatives of 3-has single-minded selectivity, and yield
Higher.
Claims (8)
1. the method that nitrone analog derivative prepares indole derivatives with symmetrical alkynes reaction,
It is characterized in that:
Nitrone analog derivative (1) and symmetrical alkynes (2) are that raw material generates the asymmetric indoles of 2,3-
Derivative (3), reaction equation is as follows:
Described metallic catalyst is the metal precursor of trivalent rhodium, silver salt and mantoquita；
Substituent R in described reactant and product1For C1-C10 alkyl, aryl or halogen, virtue
Base is the aryl on phenyl or phenyl ring with substituent；R2For C1-C10 alkyl or containing miscellaneous former
The heteroaryl perfume base of sub-O or S, aryl or halogen, heteroaryl perfume base is thienyl or furyl,
Aryl is the aryl on phenyl or phenyl ring with substituent；R3For C4-C10 alkyl or containing miscellaneous
The heteroaryl perfume base of atom O or S, aryl, heteroaryl perfume base is thienyl or furyl, aryl
For the aryl with substituent on phenyl or phenyl ring.
2. in accordance with the method for claim 1, it is characterised in that:
Described solvent is oxolane, 1,4-dioxane, glycol dimethyl ether, ethylene glycol
Diethyl ether, 1,2-dichloroethanes, 1, one or two or more kinds in 3-dichloropropane, the use of solvent
Amount is every 0.25 mM of reactant (2) 14 milliliters.
3. in accordance with the method for claim 1, it is characterised in that: described reaction temperature
It is 60 120 DEG C.
4. in accordance with the method for claim 1, it is characterised in that: described catalyst is adopted
By in-situ preparation method, under argon shield, rhodium salt metal precursor and silver salt in molar ratio
1:4, adds mantoquita after stirring 20-30 minute in solvent at room temperature.
5. according to the method described in claim 1 or 4, it is characterised in that: before described metal
Body is that dichloro (pentamethylcyclopentadiene base) closes rhodium (III) dimer ([RhCp*Cl2]2)；Silver salt is
Silver hexafluoroantimonate or silver trifluoromethanesulfonate；Mantoquita is Salicylaldoxime and/or acetic anhydride is cuprous.
6. according to the method described in claim 1 or 4, it is characterised in that: described addition
Rhodium metal precursor mole is 2.5% to the 5% of symmetrical alkynes (2), the mole dosage of silver salt
For 10% to the 20% of symmetrical alkynes (2), the mole dosage of mantoquita is symmetrical alkynes (2)
1-2 times amount.
7. in accordance with the method for claim 1, it is characterised in that: the reaction time is that 6-16 is little
When.
8. in accordance with the method for claim 1, it is characterised in that: described nitrone class is spread out
The mole dosage of biological (1) and symmetrical alkynes (2) ratio is for 1.2:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214252A (en) * | 2021-05-28 | 2021-08-06 | 常州大学 | Synthesis method of 6-phenyl-7- (pyridine-2-yl) -7H-indolo [2,3-c ] quinoline compound |
| CN115677588A (en) * | 2021-07-30 | 2023-02-03 | 中国科学院成都有机化学有限公司 | 2,3,5,5-tetrasubstituted-4-carbonyl imidazole cyclic nitrone compound, preparation method and application |
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| WO2008094922A1 (en) * | 2007-01-31 | 2008-08-07 | Philadelphia Health & Education Corporation, D/B/A Drexel University College Of Medicine | Photolabile dinitroindolinyl based compounds |
| CN103755621A (en) * | 2014-01-23 | 2014-04-30 | 清华大学 | Method for preparing polysubstituted indole from aryl hydrazine and alkyne |
| CN103772233A (en) * | 2014-01-06 | 2014-05-07 | 华东师范大学 | Multi-halothane five-member cyclic nitrone derivative and preparation method thereof |
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Patent Citations (3)
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| WO2008094922A1 (en) * | 2007-01-31 | 2008-08-07 | Philadelphia Health & Education Corporation, D/B/A Drexel University College Of Medicine | Photolabile dinitroindolinyl based compounds |
| CN103772233A (en) * | 2014-01-06 | 2014-05-07 | 华东师范大学 | Multi-halothane five-member cyclic nitrone derivative and preparation method thereof |
| CN103755621A (en) * | 2014-01-23 | 2014-04-30 | 清华大学 | Method for preparing polysubstituted indole from aryl hydrazine and alkyne |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214252A (en) * | 2021-05-28 | 2021-08-06 | 常州大学 | Synthesis method of 6-phenyl-7- (pyridine-2-yl) -7H-indolo [2,3-c ] quinoline compound |
| CN113214252B (en) * | 2021-05-28 | 2022-02-11 | 常州大学 | Synthesis method of 6-phenyl-7- (pyridine-2-yl) -7H-indolo [2,3-c ] quinoline compound |
| CN115677588A (en) * | 2021-07-30 | 2023-02-03 | 中国科学院成都有机化学有限公司 | 2,3,5,5-tetrasubstituted-4-carbonyl imidazole cyclic nitrone compound, preparation method and application |
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