CN106632329A - Indole derivative with pyridine-piperidine-indole ring structure and synthesis method of indole derivative - Google Patents
Indole derivative with pyridine-piperidine-indole ring structure and synthesis method of indole derivative Download PDFInfo
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Abstract
The invention belongs to the technical field of medicine, and particularly relates to an indole derivative with a pyridine-piperidine-indole ring structure and a synthesis method of the indole derivative. N-pyridinyl indole, diphenyl acetylene, a cobalt catalyst, silver acetate (AgOAc), cupric acetate monohydrate (Cu(OAc)2.H2O), silver tetrafluoroborate (AgBF4) and an organic solvent are sequentially added to a reaction tube under the protection of inert gas; the components are stirred and react at the temperature of 130-140 DEG C for 16-30 h, pyridino[2',1:2,3]piperidine[1,6-a]indole salt is obtained; absolute methanol and sodium borohydride are added, all components are stirred and react at the temperature of 5 DEG C or lower for 1.5-2.5 h, and a target product is obtained. The target product is an important alkaloid and has higher biological activity and even pharmaceutical value, and the synthesis method has the advantages that the steps are simple and the yield is high.
Description
Technical field
The invention belongs to pharmaceutical technology field, and in particular to the indole derivatives of a kind of pyridine piperidines indoles and ring structure and
Its synthetic method.
Background technology
The indole derivatives of pyridine piperidines indoles and ring structure is living with important biology as a kind of important alkaloid
Property and certain medical value.Pyridine piperidines indoles and ring structure indole derivatives (the double hydrogen -4H- pyridos of 6,7- [2 ',
1’:2,3] piperidines simultaneously [1,6-a] indole derivatives) it is a kind of new alkaloid, it is not yet reported that this biology in prior art
Alkali and its synthetic method.
Chinese patent CN102741251B disclose a kind of pyridine cyclo-derivative, its pharmaceutically acceptable salt, its stand
Body isomers or its solvated compounds：Wherein R1, R2, R3, Q, X and Y are defined as in the description；The invention further relates to these changes
The preparation method of compound, the pharmaceutical composition containing these compounds, and these compounds are preparing treatment and/or are preventing non-
Application in IDD, hyperglycaemia, high fat of blood, the medicine of insulin resistance.But, above-mentioned patent step is answered
It is miscellaneous, low yield.
The content of the invention
To overcome drawbacks described above, it is an object of the invention to provide the indoles of a kind of pyridine piperidines indoles and ring structure derives
Thing and its synthetic method.
For achieving the above object, the present invention is adopted the following technical scheme that：
The indole derivatives of a kind of pyridine piperidines indoles and ring structure, its chemical structure of general formula is：
Wherein, the R1For a kind of in hydrogen, alkyl, halogen, alkoxyl and ester group, R2For a kind of in hydrogen, alkyl and halogen,
R3For one kind in hydrogen, alkyl, halogen and nitro.
A kind of synthetic method of the indole derivatives of above-mentioned pyridine piperidines indoles and ring structure, comprises the following steps：
(1) under inert gas shielding, N- pyridine radicals indoles, tolans, Co catalysts, vinegar are sequentially added in reaction tube
Sour silver AgOAc, water acetic acid copper Cu (OAc)2·H2O, silver tetrafluoroborate AgBF4And organic solvent；
(2) stirring reaction 16-30h under the conditions of step (1) reaction tube being placed in into 130-140 DEG C；
(3) after completion of the reaction, reaction tube is cooled to room temperature to step (2), and by reactant mixture desalination, washing, concentration is pure
Change, obtain pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding boron hydrogen
Change sodium, stirring reaction 1.5-2.5h under the conditions of temperature≤5 DEG C；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, extraction, salt solution
Washing, is dried, and purifying obtains target product.
Preferably, step (1) the N- pyridine radicals indoles, tolans, Co catalysts, silver acetate, a water acetic acid copper, four
Silver fluoborate, the amount ratio of the material of sodium borohydride are：1:1-1.2:0.018-0.022：0.036-0.043:0.9-1.1:0.9-
1.1：3.5-4.5, the N- pyridine radicals indoles is 1mmol with the amount ratio of organic solvent：8-15mL.
Preferably, step (1) Co catalysts are CoCp (CO) I2。
Preferably, step (1) organic solvent is 1,2- dichloroethanes.
Preferably, step (3) washer solvent is methyl alcohol or dichloromethane.
Preferably, step (5) the extraction solvent is methyl alcohol or dichloromethane.
Preferably, step (3) purifying is silicagel column column chromatography, and column chromatography condition is：200-300 mesh silica gel, wash-out
Agent is dichloromethane and methyl alcohol mixed solution, and both volume ratios are 20：1.
Preferably, step (5) purifying is silicagel column column chromatography, and column chromatography condition is：200-300 mesh silica gel, wash-out
Agent is n-hexane and ethyl acetate mixture, and both volume ratios are 50：1.
The synthetic method of the indole derivatives of pyridine piperidines indoles of the present invention and ring structure, its reaction expression is as follows：
Wherein, the R1For a kind of in hydrogen, alkyl, halogen, alkoxyl and ester group, R2For a kind of in hydrogen, alkyl and halogen,
R3For one kind in hydrogen, alkyl, halogen and nitro.
The positive beneficial effect of the present invention：
1. the indole derivatives of pyridine piperidines indoles of the present invention and ring structure is nitrogen-containing heterocycle compound, is a kind of important
Alkaloid, with high biologically active and medical value, and the indole derivatives of pyridine piperidines indoles of the present invention and ring structure
Synthetic method step it is simple, yield more than 66%, high income.
Specific embodiment
With reference to some specific embodiments, the present invention is further described.
Embodiment 1
The indole derivatives of a kind of pyridine piperidines indoles and ring structure, its chemical structure of general formula is：
The synthetic method of the indole derivatives of above-mentioned pyridine piperidines indoles and ring structure, comprises the following steps：
(1) under nitrogen protection, N- pyridine radicals indoles 0.20mmol, tolans are sequentially added in schlenk pipes
0.2mmol, Co catalysts CoCp (CO) I2The water acetic acid copper Cu of 1.8mol%, silver acetate AgOAc 3.6mol%, one
(OAc)2·H2O 0.22mmol, silver tetrafluoroborate AgBF40.22mmol and 1,2- dichloroethanes 3mL；
(2) step (1) reaction tube is placed in into stirring reaction 30h under the conditions of 130 DEG C of oil baths；
(3) after completion of the reaction, reaction tube is cooled to room temperature, and reactant mixture desalination is washed with dichloromethane, concentration,
Column chromatography condition is purified, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is dichloromethane and methyl alcohol mixed solution, both
Volume ratio is 20：1, obtain pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding boron hydrogen
Change sodium 0.9mmol, stirring reaction 1.5h under the conditions of 2 DEG C of temperature；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, is extracted with methyl alcohol
Take, salt water washing, be dried, silicagel column column chromatography is purified, column chromatography condition is：200-300 mesh silica gel, eluant, eluent be n-hexane and
Ethyl acetate mixture, both volume ratios are 50：1, obtain target product colorless solid 55.2mg, yield 71%, mp.91-
93℃.1H NMR (400MHz, CDCl3) δ 7.26-6.79 (m, 13H), 5.85 (dd, J=16.7,13.9Hz, 3H), 5.58 (d,
J=9.7Hz, 1H), 3.68 (q, J=18.5Hz, 2H), 2.93-2.67 (m, 1H), 2.48-2.01 (m, 4H) .13C NMR
(101MHz,CDCl3)δ141.34,137.59,136.30,135.15,132.69,132.07,131.41,130.29,
130.11,129.04,128.71,127.88,127.72,127.49,127.45,125.82,125.73,122.25,119.67,
107.67,107.01,95.92,67.02,49.05,26.28,21.49.HRMS m/z(ESI)Calcd for C28H25N2[M
+H+],389.2012,found 389.2017。
Embodiment 2
The indole derivatives of a kind of pyridine piperidines indoles and ring structure, its chemical structure of general formula is：
The synthetic method of the indole derivatives of above-mentioned pyridine piperidines indoles and ring structure, comprises the following steps：
(1) under nitrogen protection, N- pyridine radicals indoles 0.20mmol, tolans are sequentially added in schlenk pipes
0.22mmol, Co catalysts CoCp (CO) I2The water acetic acid copper Cu of 2.0mol%, silver acetate AgOAc 4.0mol%, one
(OAc)2·H2O 0.20mmol, silver tetrafluoroborate AgBF40.20mmol and 1,2- dichloroethanes 2mL；
(2) step (1) reaction tube is placed in into stirring reaction 24h under the conditions of 135 DEG C of oil baths；
(3) after completion of the reaction, reaction tube is cooled to room temperature, and reactant mixture desalination is washed with dichloromethane, concentration,
Column chromatography condition is purified, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is dichloromethane and methyl alcohol mixed solution, both
Volume ratio is 20：1, obtain pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding boron hydrogen
Change sodium 0.8mmol, stirring reaction 2h under the conditions of 0 DEG C of temperature；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, uses dichloromethane
Extraction, salt water washing is dried, silicagel column column chromatography purifying, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is n-hexane
And ethyl acetate mixture, both volume ratios are 50：1, obtain target product colorless solid 63.0mg, yield 77%,
mp.100-102℃.1H NMR(400MHz,CDCl3)δ7.37(s,1H),7.25(s,1H),7.23-6.90(m,11H),6.01-
5.82 (m, 3H), 5.68 (d, J=10.0Hz, 1H), 3.77 (q, J=18.7Hz, 2H), 3.31-2.72 (m, 1H), 2.32 (d, J
=16.7Hz, 1H).13C NMR(101MHz,CDCl3)δ142.23,137.43,137.16,134.78,132.63,131.33,
130.88,130.12,127.95,127.89,127.59,127.46,126.00,125.53,125.44,120.74,119.05,
108.70,106.42,95.66,66.99,49.05,26.28.HRMS m/z(ESI)Calcd for C27H22N2Cl[M+H+],
409.1472,found 409.1477。
Embodiment 3
The indole derivatives of a kind of pyridine piperidines indoles and ring structure, its chemical structure of general formula is：
The synthetic method of the indole derivatives of above-mentioned pyridine piperidines indoles and ring structure, comprises the following steps：
(1) under nitrogen protection, N- pyridine radicals indoles 0.20mmol, tolans are sequentially added in schlenk pipes
0.22mmol, Co catalysts CoCp (CO) I2The water acetic acid copper Cu of 2.0mol%, silver acetate AgOAc 4.0mol%, one
(OAc)2·H2O 0.20mmol, silver tetrafluoroborate AgBF40.20mmol and 1,2- dichloroethanes 2mL；
(2) step (1) reaction tube is placed in into stirring reaction 24h under the conditions of 135 DEG C of oil baths；
(3) after completion of the reaction, reaction tube is cooled to room temperature, and reactant mixture desalination is washed with dichloromethane, concentration,
Column chromatography condition is purified, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is dichloromethane and methyl alcohol mixed solution, both
Volume ratio is 20：1, obtain pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding boron hydrogen
Change sodium 0.8mmol, stirring reaction 2h under the conditions of 0 DEG C of temperature；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, uses dichloromethane
Extraction, salt water washing is dried, silicagel column column chromatography purifying, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is n-hexane
And ethyl acetate mixture, both volume ratios are 50：1, obtain target product colorless solid, 69.6mg, yield 86%,
mp.99-101℃.1H(400MHz,CDCl3) δ 7.25 (s, 1H), 7.23-7.00 (m, 10H), 6.92 (s, 1H), 6.78 (d, J=
8.6Hz, 1H), 6.34-5.80 (m, 3H), 5.67 (d, J=9.7Hz, 1H), 4.08-3.50 (m, 5H), 2.90 (t, J=
16.3Hz, 1H), 2.33 (d, J=16.3Hz, 1H).13CNMR(101MHz,CDCl3)δ154.38,141.38,137.49,
136.91,135.06,131.38,130.31,130.25,129.57,127.88,127.74,127.49,127.42,125.83,
125.68,110.37,108.55,106.90,102.22,96.14,67.12,55.88,49.03,26.28.HRMS m/z
(ESI)Calcd for C28H25N2O[M+H+],405.1961,found 405.1966。
Embodiment 4
The indole derivatives of a kind of pyridine piperidines indoles and ring structure, its chemical structure of general formula is：
The synthetic method of the indole derivatives of above-mentioned pyridine piperidines indoles and ring structure, comprises the following steps：
(1) under nitrogen protection, N- pyridine radicals indoles 0.20mmol, tolans are sequentially added in schlenk pipes
0.22mmol, Co catalysts CoCp (CO) I2The water acetic acid copper Cu of 2.0mol%, silver acetate AgOAc 4.0mol%, one
(OAc)2·H2O 0.20mmol, silver tetrafluoroborate AgBF40.20mmol and 1,2- dichloroethanes 2mL；
(2) step (1) reaction tube is placed in into stirring reaction 24h under the conditions of 135 DEG C of oil baths；
(3) after completion of the reaction, reaction tube is cooled to room temperature, and reactant mixture desalination is washed with dichloromethane, concentration,
Column chromatography condition is purified, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is dichloromethane and methyl alcohol mixed solution, both
Volume ratio is 20：1, obtain pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding boron hydrogen
Change sodium 0.8mmol, stirring reaction 2h under the conditions of 0 DEG C of temperature；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, uses dichloromethane
Extraction, salt water washing is dried, silicagel column column chromatography purifying, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is n-hexane
And ethyl acetate mixture, both volume ratios are 50：1, obtain target product colorless solid, 63.6mg, yield 81%,
mp.99-101℃.1H NMR(400MHz,CDCl3) δ 7.18-6.99 (m, 12H), 6.77 (td, J=9.1,2.0Hz, 1H),
5.88-5.78 (m, 2H), 5.60 (d, J=10.0Hz, 1H), 3.69 (q, J=18.7Hz, 2H), 2.90-2.77 (m, 1H),
2.25 (d, J=16.8Hz, 1H).13C NMR(101MHz,CDCl3) δ 158.19 (d, J=233.9Hz), 137.24,134.84,
131.36,130.15,127.95,127.91,127.87,127.57,127.46,125.97,125.59,108.55 (d, J=
26.3Hz), 108.20 (d, J=9.9Hz), 104.84,104.72 (d, J=23.7Hz), 67.08,48.96,26.18.HRMS
m/z(ESI)Calcd for C27H22FN2[M+H+],393.1762,found 393.1767。
Embodiment 5
The indole derivatives of a kind of pyridine piperidines indoles and ring structure, its chemical structure of general formula is：
The synthetic method of the indole derivatives of above-mentioned pyridine piperidines indoles and ring structure, comprises the following steps：
(1) under nitrogen protection, N- pyridine radicals indoles 0.20mmol, tolans are sequentially added in schlenk pipes
0.24mmol, Co catalysts CoCp (CO) I2The water acetic acid copper Cu of 2.2mol%, silver acetate AgOAc 4.3mol%, one
(OAc)2·H2O 0.18mmol, silver tetrafluoroborate AgBF40.18mmol and 1,2- dichloroethanes 1.6mL；
(2) step (1) reaction tube is placed in into stirring reaction 16h under the conditions of 140 DEG C of oil baths；
(3) after completion of the reaction, reaction tube is cooled to room temperature, and reactant mixture desalination is washed with methyl alcohol, concentration, post layer
Analysis condition is purified, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is dichloromethane and methyl alcohol mixed solution, both volumes
Than for 20：1, obtain pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding boron hydrogen
Change sodium 0.7mmol, stirring reaction 2.5h under the conditions of 5 DEG C of temperature；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, is extracted with methyl alcohol
Take, salt water washing, be dried, silicagel column column chromatography is purified, column chromatography condition is：200-300 mesh silica gel, eluant, eluent be n-hexane and
Ethyl acetate mixture, both volume ratios are 50：1, obtain target product colorless solid, 53.1mg, 66%, mp.99-101
℃.1H NMR(400MHz,CDCl3) δ 7.34 (t, J=7.8Hz, 1H), 7.15 (d, J=6.0Hz, 1H), 7.02 (dd, J=
16.1,7.7Hz, 2H), 6.98-6.89 (m, 6H), 6.85 (d, J=7.6Hz, 2H), 6.03-5.73 (m, 2H), 5.59 (d, J=
9.9Hz, 1H), 3.67 (q, J=18.8Hz, 2H), 2.99-2.68 (m, 1H), 2.33-2.30 (m, 1H), 2.19 (s, 6H).13C
NMR(101MHz,CDCl3)δ141.20,137.41,135.00,134.63,134.11,132.05,131.17,129.90,
129.60,128.62,128.50,128.17,127.44,125.64,120.54,119.76,119.63,108.03,106.63,
95.86,66.86,49.05,26.29,21.27,21.15.HRMS m/z(ESI)Calcd for C29H27N2[M+H+],
403.2169,found 403.2166。
Biological activity test
1. experiment material：DPPH free radicals, vitamin C, ultraviolet specrophotometer.
2. experimental procedure：A. the pyridine piperidines indoles and ring structure of precise 2.0mg embodiment of the present invention 1-5 are distinguished
Indole derivatives, with anhydrous ethanol solvent l0mL is settled to, and the sample prepare liquid that concentration is 0.20mg/mL is configured to respectively, will
It is standby that above-mentioned prepare liquid is diluted to series concentration by 2 times, 4 times, 8 times, 16 times, 32 times, 64 times, 128 times；Precise again
2.0mg vitamin Cs, are equally settled to l0mL with anhydrous ethanol solvent, and the positive control sample for being configured to 0.20mg/mL is to be measured
Liquid；If absolute ethyl alcohol is blank.
B. precise 8.5mg DPPH, it is 0.085mg/mL solution for standby to be configured to concentration with dichloromethane, meanwhile, it is accurate
Each prepare liquid 2mL is really weighed, the DPPH solution (0.085mg/mL) of 2mL is separately added into, 30min is stood after shaking up, at 517nm
Mensuration absorbance, calculates clearance rate of each compound to DPPH free radicals, and experimental result is shown in Table 1.
DPPH free radical scavenging activity computing formula：Clearance rate (%)=[1- (A1-A2)/A3] × 100%,
Wherein, A1-2mL samples prepare liquid+2mLDPPH solution, A2-2mL sample prepare liquid+2mL absolute ethyl alcohols, A3-2mL
DPPH solution+2mL absolute ethyl alcohols.
Clearance rate (n=6) of the indole derivatives of embodiment 1-5 of table 1 to DPPH free radicals
Note：* P ＜ 0.01 are represented.
As shown in Table 1, the indole derivatives of the pyridine piperidines indoles of embodiment of the present invention 1-5 and ring structure is to DPPH freedom
Base has obvious scavenging action, hence it is evident that be better than positive control drug vitamin C, therefore, the pyridine piperidines of embodiment of the present invention 1-5
The very strong biologically active of the indole derivatives of indoles and ring structure.
Claims (9)
1. the indole derivatives of a kind of pyridine piperidines indoles and ring structure, it is characterised in that its chemical structure of general formula is：
Wherein, the R1For a kind of in hydrogen, alkyl, halogen, alkoxyl and ester group, R2For a kind of in hydrogen, alkyl and halogen, R3For
It is a kind of in hydrogen, alkyl, halogen and nitro.
2. the synthetic method of the indole derivatives of the pyridine piperidines indoles described in a kind of claim 1 and ring structure, its feature exists
In comprising the following steps：
(1) under inert gas shielding, N- pyridine radicals indoles, tolans, Co catalysts, silver acetate are sequentially added in reaction tube
AgOAc, water acetic acid copper Cu (OAc)2·H2O, silver tetrafluoroborate AgBF4And organic solvent；
(2) stirring reaction 16-30h under the conditions of step (1) reaction tube being placed in into 130-140 DEG C；
(3) after completion of the reaction, reaction tube is cooled to room temperature to step (2), and reactant mixture desalination, washing, concentration, purifying are obtained
To pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt；
(4) by pyrido [2', 1':2,3] piperidines [1,6-a] indoles salt is dissolved in absolute methanol, is subsequently adding sodium borohydride,
Stirring reaction 1.5-2.5h under the conditions of temperature≤5 DEG C；
(5) after step (4) reaction terminates, reaction tube is cooled to room temperature, and reactant mixture is added water extraction liquid, extraction, salt water washing,
It is dried, purifying obtains target product.
3. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (1) the N- pyridine radicals indoles, tolans, Co catalysts, silver acetate, a water acetic acid copper, silver tetrafluoroborate, boron
The amount ratio of the material of sodium hydride is：1:1-1.2:0.018-0.022：0.036-0.043:0.9-1.1:0.9-1.1：3.5-4.5,
The N- pyridine radicals indoles is 1mmol with the amount ratio of organic solvent：8-15mL.
4. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (1) Co catalysts are CoCp (CO) I2。
5. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (1) organic solvent is 1,2- dichloroethanes.
6. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (3) washer solvent is methyl alcohol or dichloromethane.
7. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (5) the extraction solvent is methyl alcohol or dichloromethane.
8. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (3) purifying is silicagel column column chromatography, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent is dichloromethane
With methyl alcohol mixed solution, both volume ratios are 20：1.
9. the synthetic method of the azole derivatives of pyridine piperidines indoles according to claim 2 and ring structure, its feature exists
In step (5) purifying is silicagel column column chromatography, and column chromatography condition is：200-300 mesh silica gel, eluant, eluent be n-hexane and
Ethyl acetate mixture, both volume ratios are 50：1.
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Non-Patent Citations (5)
| Title |
|---|
| MANA YAMASHITA等: "Fused Ring Construction around Pyrrole, Indole, and Related Compounds via Palladium-Catalyzed Oxidative Coupling with Alkynes", 《J. ORG. CHEM.》 * |
| MANA YAMASHITA等: "Synthesis of Condensed Heteroaromatic Compounds by Palladium-Catalyzed Oxidative Coupling of Heteroarene Carboxylic Acids with Alkynes", 《ORGANIC LETTERS》 * |
| SEKAR PRAKASH等: "Cobalt-Catalyzed Oxidative Annulation of Nitrogen-Containing Arenes with Alkynes: An Atom-Economical Route to Heterocyclic Quaternary Ammonium Salts", 《ANGEW. CHEM. INT. ED.》 * |
| XINGYAN LIU等: "Aldehyde as a Traceless Directing Group for Rh(III)-Catalyzed C−H Activation: A Facile Access to Diverse Indolo[1,2 a]quinolines", 《ORG. LETT.》 * |
| YE-XING LAO等: "High-Valent Pentamethylcyclopentadienylcobalt(III) or -iridium(III)-Catalyzed CÿH Annulation with Alkynes: Synthesis of Heterocyclic Quaternary Ammonium Salts", 《ADV. SYNTH. CATAL.》 * |
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