CN105985279B - A kind of method that nitrone analog derivative prepares indole derivatives with symmetrical alkynes reaction - Google Patents
A kind of method that nitrone analog derivative prepares indole derivatives with symmetrical alkynes reaction Download PDFInfo
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- CN105985279B CN105985279B CN201510058946.8A CN201510058946A CN105985279B CN 105985279 B CN105985279 B CN 105985279B CN 201510058946 A CN201510058946 A CN 201510058946A CN 105985279 B CN105985279 B CN 105985279B
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Abstract
The present invention relates to a kind of methods for preparing indole derivatives by nitrone analog derivative and symmetrical alkynes reaction, specifically react the new method for preparing 2,3 asymmetric indole derivativeses with symmetrical alkynes under the catalysis of trivalent rhodium by nitrone compound.The present invention obtains 2,3 asymmetric indole derivativeses using transition-metal catalyst, through shirtsleeve operation step, good reaction selectivity, and yield is higher.
Description
Technical field
Indoles is prepared by nitrone analog derivative and symmetrical alkynes reaction under transition metal rhodium catalysis the present invention relates to one kind
The method of derivative.
Background technology
Indoles is one of most important heterocycle, is widely present in natural products, medicine and functional material (document 1：(a)
Sundberg,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.).There is three classes side by the method that metal catalytic carries out indole synthesis
Method：Method one：(document 2 is prepared by classical nucleophilic addition：(a)Kraus,G.A.；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：Structure
Nitrogenous guiding group, the C-H activations synthesis of indole (document 3 through transition metal：(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 prepares the new of indole derivatives by transition metal rhodium catalysis through nitrone analog derivative and symmetrical alkynes reaction
Method.This method can be through the indole derivatives that the synthesis 2,3 of step selectivity is different substituents, high income, operation letter
List and raw material is cheap and easy to get.
The content of the invention
It is an object of the invention to provide a kind of method of synthesis of indole derivative, nitrone analog derivative is with symmetrical alkynes
Raw material generates the asymmetric indole derivativeses of 2,3-, and reaction equation is as follows：
The metallic catalyst is metal precursor, silver salt and the mantoquita of trivalent rhodium；
Substituent R in the reactant and product1For C1-C10 alkyl, aryl or halogen, aryl is on phenyl or phenyl ring
Aryl with substituent group；R2Heteroaryl perfume base, aryl or halogen for C1-C10 alkyl or containing hetero atom O or S, heteroaryl perfume base
For thienyl or furyl, aryl is the aryl with substituent group on phenyl or phenyl ring；R3For C4-C10 alkyl or contain miscellaneous original
Heteroaryl perfume base, the aryl of sub- O or S, heteroaryl perfume base are thienyl or furyl, and aryl is with substituent group on phenyl or phenyl ring
Aryl.
The solvent is tetrahydrofuran, 1,4- dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, 1,2- dichloros
One or two or more kinds in ethane, 1,3- dichloropropanes, the dosage of solvent is every (2) 1-4 milliliters of 0.25 mM of reactant.
The reaction temperature is 60-120 DEG C；When the reaction time is 6-16 small.
The catalyst uses in-situ preparation method, and under protection of argon gas, rhodium salt metal precursor and silver salt are pressed mole
Than 1:4, add in mantoquita after stirring 20-30 minutes in solvent at room temperature.
The metal precursor closes rhodium (III) dimer ([RhCp*Cl for dichloro (pentamethylcyclopentadiene base)2]2)；Silver salt
For silver hexafluoroantimonate or silver trifluoromethanesulfonate；Mantoquita is cuprous for Salicylaldoxime and/or acetic anhydride；The rhodium metal precursor of addition
Mole is 2.5% to the 5% of symmetrical alkynes, and the mole dosage of silver salt is 10% to the 20% of symmetrical alkynes, mole of mantoquita
Dosage is 1-2 times of symmetrical alkynes and measures.
The mole dosage ratio of the nitrone analog derivative and symmetrical alkynes is 1.2:1.
The invention has the advantages that：
1. reactant nitrone is obtained by raw material aldehyde cheap and easy to get, nitrobenzene through simple reaction step；Symmetrical alkynes is by holding
Alkynes is obtained through simple reaction step, and raw material is simple and easy to get.
2. reaction it is transition metal-catalyzed it is lower just obtain 2,3 different disubstituted indole derivativeses in high yield through a step,
It is easy to operate efficient.
Description of the drawings
Fig. 1 is compound 3a's1H NMR spectras；
Fig. 2 is compound 3a's13C NMR spectras；
Fig. 3 is compound 3b's1H NMR spectras；
Fig. 4 is compound 3b's13C NMR spectras；
Fig. 5 is compound 3c's1H NMR spectras；
Fig. 6 is compound 3c's13C NMR spectras；
Fig. 7 is compound 3d's1H NMR spectras；
Fig. 8 is compound 3d's13C NMR spectras.
Specific embodiment
For a better understanding of the present invention, illustrated by following instance.
Embodiment 1
It is reacted in reactor, reactor leads to argon gas displacement three times after vacuumizing after, adds in rhodium salt metal precursor
(0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6mg), 2 milliliters of dioxane, after stirring 30 minutes,
Addition Salicylaldoxime (0.25mmol, 45.4mg), nitrone 1a (0.3mmol, 68.1mg) and symmetrical alkynes 2a (0.25mmol,
44.5mg), be stirred to react at 100 DEG C 16 it is small when.After reaction, solvent is taken out with Rotary Evaporators, then column chromatography for separation,
Eluant, eluent is petroleum ether：Ethyl acetate=20:1 mixed solvent obtains the indoles 3a of 60.5mg.Separation yield is 81%.
The characterize data of compound 3a is 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
It is reacted in reactor, reactor leads to argon gas displacement three times after vacuumizing after, adds in rhodium salt metal precursor
(0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6mg), 2 milliliters of dioxane, after stirring 30 minutes,
Addition Salicylaldoxime (0.25mmol, 45.4mg), nitrone 1b (0.3mmol, 72.3mg) and symmetrical alkynes 2a (0.25mmol,
44.5mg), be stirred to react at 100 DEG C 16 it is small when.After reaction, solvent is taken out with Rotary Evaporators, then column chromatography for separation,
Eluant, eluent is petroleum ether：Ethyl acetate=20:1 mixed solvent obtains the indoles 3b of 64.2mg.Separation yield is 82%.
The characterize data of compound 3b is 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 spectrogram is shown in specification to .4,21.7.
Attached drawing 4)
Embodiment 3
It is reacted in reactor, reactor leads to argon gas displacement three times after vacuumizing after, adds in rhodium salt metal precursor
(0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6mg), 2 milliliters of dioxane, after stirring 30 minutes,
Addition Salicylaldoxime (0.25mmol, 45.4mg), nitrone 1c (0.3mmol, 82.8mg) and symmetrical alkynes 2a (0.25mmol,
44.5mg), be stirred to react at 100 DEG C 16 it is small when.After reaction, solvent is taken out with Rotary Evaporators, then column chromatography for separation,
Eluant, eluent is petroleum ether：Ethyl acetate=20:1 mixed solvent obtains the indoles 3c of 56.6mg.Separation yield is 65%.
The characterize data of compound 3c is 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 Figure of description 5)
13C NMR(100MHz,CDCl3)δ136.1,134.3,132.9,132.0,131.8,130.2,129.74,
(128.9,128.8,126.6,123.2,121.9,120.8,119.9,111.1. spectrogram is shown in Figure of description 6)
Embodiment 4
It is reacted in reactor, reactor leads to argon gas displacement three times after vacuumizing after, adds in rhodium salt metal precursor
(0.00625mmol, 3.9mg) and silver hexafluoroantimonate (0.025mmol, 8.6mg), 2 milliliters of dioxane, after stirring 30 minutes,
Addition Salicylaldoxime (0.25mmol, 45.4mg), nitrone 1d (0.3mmol, 59.1mg) and symmetrical alkynes 2b (0.25mmol,
59.5mg), be stirred to react at 100 DEG C 16 it is small when.After reaction, solvent is taken out with Rotary Evaporators, then column chromatography for separation,
Eluant, eluent is petroleum ether：Ethyl acetate=20:1 mixed solvent obtains the indoles 3d of 60.5mg.Separation yield is 81%.
The characterize data of compound 3d is 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=8.6Hz, 2H), 3.84 (s, 3H)；(spectrogram is shown in that specification is attached
Fig. 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)
By above example and each collection of illustrative plates as it can be seen that method provided by the invention is raw materials used simple and easy to get, react to preparing
2,3- asymmetric indole derivativeses have single-minded selectivity, and yield is higher.
Claims (7)
1. a kind of method that nitrone analog derivative prepares indole derivatives with symmetrical alkynes reaction, it is characterised in that：
Nitrone analog derivative (1) generates the asymmetric indole derivativeses of 2,3- (3), reaction equation with symmetrical alkynes (2) for raw material generation
It is as follows：
The metallic catalyst is metal precursor, silver salt and the mantoquita of trivalent rhodium, and the metal precursor is dichloro (pentamethyl ring penta
Dialkylene) close rhodium (III) dimer ([RhCp*Cl2]2)；Silver salt is silver hexafluoroantimonate or silver trifluoromethanesulfonate；Mantoquita is anhydrous
Copper acetate or acetic anhydride are cuprous；
Substituent R in the reactant and product1For C1-C10 alkyl, aryl or halogen, aryl takes to be carried on phenyl or phenyl ring
The aryl of Dai Ji；R2Heteroaryl perfume base, aryl or halogen for C1-C10 alkyl or containing hetero atom O or S, heteroaryl perfume base are thiophene
Base or furyl, aryl are the aryl with substituent group on phenyl or phenyl ring；R3For C4-C10 alkyl or contain hetero atom O or S
Heteroaryl perfume base, aryl, heteroaryl perfume base is thienyl or furyl, and aryl is carries the aryl of substituent group on phenyl or phenyl ring.
2. according to the method for claim 1, it is characterised in that：
The solvent for tetrahydrofuran, 1,4- dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, 1,2- dichloroethanes,
One or two or more kinds in 1,3- dichloropropane, the dosage of solvent is every (2) 1-4 milliliters of 0.25 mM of reactant.
3. according to the method for claim 1, it is characterised in that：Reaction temperature is 60-120 DEG C.
4. according to the method for claim 1, it is characterised in that：Catalyst uses in-situ preparation method, under protection of argon gas,
Rhodium salt metal precursor and silver salt in molar ratio 1:4, add in mantoquita after stirring 20-30 minutes in solvent at room temperature.
5. according to the method described in claim 1 or 4, it is characterised in that：The rhodium metal precursor mole is symmetrical alkynes (2)
2.5% to 5%, the mole dosage of silver salt is 10% to the 20% of symmetrical alkynes (2), and the mole dosage of mantoquita is symmetrical alkynes
(2) 1-2 times is measured.
6. according to the method for claim 1, it is characterised in that：When reaction time is 6-16 small.
7. according to the method for claim 1, it is characterised in that：The nitrone analog derivative (1) and symmetrical alkynes (2)
Mole dosage ratio is 1.2:1.
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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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
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| N-alkenyl nitrone dipolar cycloaddition routes to piperidines and indolizidines .8. the scope of tandem reactions involving hydroxylamine-alkyne cyclisations;Davison, EC，等;《TETRAHEDRON》;19960826;第52卷(第35期);第11601-11624页 * |
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