CN104177357B - A kind of method of synthesis isoquinolin salt - Google Patents
A kind of method of synthesis isoquinolin salt Download PDFInfo
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- CN104177357B CN104177357B CN201310203409.9A CN201310203409A CN104177357B CN 104177357 B CN104177357 B CN 104177357B CN 201310203409 A CN201310203409 A CN 201310203409A CN 104177357 B CN104177357 B CN 104177357B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
- C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
- C07D455/04—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine
- C07D455/06—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine containing benzo [a] quinolizine ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/10—Quaternary compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
- C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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Abstract
The invention discloses a kind of preparation method of substituted isoquinolin salt.The method adopts with oxygen as oxidant, and aromatic hydrocarbons, alkynes and acid that various substituent groups replace are initiation material, by transition metal-catalyzed, obtain the compound of isoquinoline-containing salt structure.This reaction raw materials, oxidant and catalyst are cheap and easy to get, and synthesis technique is simple, greatly reduces synthesis cost；Reaction condition is gentle, yield high it is easy to industrialization；Reaction raw materials and catalyst clean are nontoxic, and environmental pollution is little.Such compound and its derivant, as important fine chemicals, obtain in industries such as medicine, pesticide, spice and photoelectricity and extensively apply.
Description
Technical field
The present invention relates to the preparation method of a kind of compound of isoquinoline-containing salt structure and the isoquinolin salt replacing, specifically
For, it is initiation material that this preparation method adopts the aromatic hydrocarbons that various substituent groups replace, alkynes and acid, is urged by transition metal
Change, obtain the compound of isoquinoline-containing salt structure, such compound can get various substituted isoquinolin by simple conversion
Class compound.
Background technology
Isoquinolin salt, as a kind of important fine chemicals, has extensive use in industries such as pesticide, medicine, spice
On the way.
Isoquinolin nitrogen heterocyclic ring is common pharmacophoric group, is widely present in and various has physiologically active natural product and conjunction
Become in medicine, be also the fragment constituting various functions material simultaneously.For example, Coralyne, it is for antiscorbutic medicine
(J.Heterocyclic Chem.1988,18, 223-232.)；5,6-dihydrocordyne, it
It is a kind of common anti-tumor agent comprising salmosin, and be a kind of camptothecine of topoisomerase；（Cancer Res.1988,48,1722-1726）；Sempervirine, it is a kind of natural alkaloid.Due to this kind of compound specific use, in recent years
Carry out people and developed substantial amounts of synthetic method, the preparation method of common report is as follows：
The method of traditional synthesis isoquinolin salt is to be reacted with halogenated aryl hydrocarbon using isoquinolin.Although the method has higher
Yield is it is not necessary to use catalyst, but the method needs by limiting that isoquinolin replaces, and practical application is subject to greatly
Limit.
For overcoming a variety of drawbacks of above-mentioned uncatalyzed reaction, the synthesis isoquinolin salt that people have developed metal catalytic derives
The method of thing, such as method 1 ~ 3, particular reference：(1) Núnez, A.; Cuadro, A. M.; Alvarez-Builla,
J.; Vaquero, J. J.Org.Lett,2007,9,2977;(2)Li,L.;Brennessel,W.W.;
Jones, W. D.J.Am.Chem.Soc.2008,130,12414；(3)Jayakumar,J.;
Parthasarathy, K.; Cheng, C.-H.Angew.Chem.Int.Ed.2012,51,
197；(4) Parthasarathy, K.; Senthilkumar, N.; Jayakumar, J.; Cheng, C.-H.Org.Lett,2012,14,3478.
Although these have improved compared with method one, yet suffer from some shortcomings.For example：Method one is although react bar
Part is gentle, however it is necessary that the reactant of costliness and catalyst, and reaction substrate is expanded and is severely limited；Method two, reaction
Although just can occur at room temperature, this reaction is equivalent reaction, and reaction needs substep to carry out, and needs substantial amounts of valuable gold
Metal catalyst, and be only capable of by the use of a kind of alkynes as reactant；Method three is although method is improved a lot, but this reaction
Need expensive metal AgBF of equivalent4Need 120 as oxidantoThe high temperature of C, Atom economy is not high.Therefore, with cleaning
Oxygen (1atm), as oxidant, is activated by C-H, and high atom economy is prepared isoquinolin salt derivative and had important theory
Meaning and be widely applied prospect.
Content of the invention
It is an object of the invention to provide a kind of preparation method being concisely and efficiently isoquinolin salt derivative.
The method that the present invention prepares isoquinolin salt derivative, is with oxygen as oxidant, and metal rhodium salt is catalyst, is having
In machine solvent, arene derivatives, alkynes are with sour with 1:1:1 mol ratio, 120o22-36 hour is reacted under C oxygen；Reaction knot
Solvent was drained, simple washing can get isoquinolin salt derivative after restrainting diatomite layer；
The structural formula of described arene derivatives is：
Wherein, X=C, N.
R1Group is each independently selected from：C1～C40Fat group（As methyl, ethyl, propyl group, isopropyl, butyl, benzyl
Base）, C4～C60Interior aromatic group（As furyl, furan derivatives base, pyridine radicals, pyridine derivate base, phenyl, substituted benzene
Base, 1- naphthyl, 2- naphthyl）, alkoxyl, hydroxyl, nitro, amido, halogen（Fluorine, chlorine, bromine, iodine）, ring-type alkynes.
The structure of described alkynes derivant is：
R2、R3For hydrogen, C1～C40Fat group（As methyl, ethyl, propyl group, isopropyl, butyl, benzyl）, C4～C60Interior
Aromatic group（As furyl, furan derivatives base, pyridine radicals, pyridine derivate base, phenyl, substituted-phenyl, 1- naphthyl, 2-
Naphthyl）, alkoxyl, hydroxyl, nitro, amido, halogen（Fluorine, chlorine, bromine, iodine）, ring-type alkynes.
Described acid（HY）For：
Various mineral acids, preferably hydrochloric acid, sulphuric acid, nitric acid, perchloric acid；Various organic acid, preferably acetic acid and anhydride, trifluoro second
Acid and anhydride, benzoic acid and its derivants, p-methyl benzenesulfonic acid and derivant, trifluoromethanesulfonic acid.Preferably acid is trifluoromethanesulfonic acid.
The pressure of described oxygen is：0.1 Mpa ~ 2.0Mpa.Preferably oxygen pressure is 1.0Mpa.
Described catalyst metals rhodium salt is：Rhodium system metal catalysts precursors, preferably rhodium chloride, trichlorine is double, and (4- methyl is different
Propyl group phenyl) rhodium, rhodium acetate, tri-chlorination two（Triphenyl phosphorus）Rhodium, tri-chlorination two（Cyclopentadiene）Rhodium and tri-chlorination two（Five first
Butylcyclopentadiene）Rhodium, ten dicarbapentaborane four rhodium, three triphenylphosphine carbonyl hydrogenation Rhs, acetylacetonatodicarrhodium rhodium, vinyl
Radium chloride, trifluoromethanesulfonic acidization three water（Cyclopentadiene）Rhodium, trifluoromethanesulfonic acidization three acetonitrile（Cyclopentadiene）Rhodium, hexafluoro-antimonic acid
Three acetonitriles（Cyclopentadiene）Rhodium.The consumption of catalyst metals rhodium salt is 0.1 % ~ 1 % of arene derivatives mole.Preferably
Catalyst metals are trifluoromethanesulfonic acidization three water（Cyclopentadiene）Rhodium.
Described solvent is：Benzene, nitromethane, toluene, benzotrifluoride, dimethylbenzene, sym-trimethylbenzene., 1,4- dioxane, second
Nitrile, propionitrile, dichloromethane, chloroform, carbon tetrachloride, 1,2- dichloroethanes, ether, glycol dimethyl ether, methyl tertiary butyl ether(MTBE), first
Cyclopentyl ether, oxolane,N ,N -Dimethylformamide,N ,N- dimethyl acetylamide, dimethyl sulfoxide, or they
Mixture.Preferably organic solvent is methanol.
The present invention has advantages below with respect to prior art：
1st, the inventive method is using industrial oxygen cheap and easy to get as oxidant, under the catalysis of metallic catalyst, by
Arene derivatives, alkynes are reacted with sour three components, by C (sp2)-H bond activation method, only one step can efficient must make
Standby isoquinolin salt derivative, this reaction raw materials and catalyst are cheap and easy to get, and synthesis technique is simple, greatly reduces synthesis cost；
2nd, the inventive method reaction condition is gentle, simple to operate, and yield is high（Up to 99 %）It is easy to industrialization；
3rd, the inventive method reaction raw materials and catalyst clean are nontoxic, and environmental pollution is little；
4th, the inventive method course of reaction cleaning, discharges with only water as garbage, more meets the requirement of Green Chemistry；
5th, this reaction transformation efficiency is higher, and the catalyst amount being used can be one thousandth, and TON is up to 740 it is easy to real
Existing industrialization.
Specific embodiment
The preparation of the present invention can be embodied as follows further with the preparation process of representational compound：
Embodiment 1, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
{[Cp*RhCl2]2(3.1 mg, 1 mol %), AgOTf (5.1 mg, 0.02 mmol), Cu (OTf)2(180.8 mg,
0.5 mmol), add in 2.0 mL methanol, under argon (1atm), 120oC react 22 hours after stopped reaction, kieselguhr mistake
Filter, dichloromethane washs, and collects organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinoline
Quinoline salt derivative 3aa.Product is white solid, yield 91%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.78 (d,J= 8.6 Hz, 1H), 9.39 (d,J=
8.3 Hz, 1H), 8.75-8.80 (m, 2H), 8.10-8.17 (m, 3H), 7.48-7.55 (m, 6H), 7.34-
7.40 (m, 3H), 7.27-7.29 (m, 2H);13C NMR (100 MHz, DMSO-d 6 ) δ 119.0, 122.2,
123.5, 124.6, 124.7, 125.9, 126.8, 128.2, 128.3, 129.3, 129.9, 130.1, 130.8,
130.9, 131.2, 132.0, 134.1, 134.4, 135.3, 136.9, 138.3, 139.9, 143.2;19F NMR
(376 MHz, DMSO-d 6 ) δ -78.02; HRMS (ESI) calcd. for C25H18N+[M-OTf]: 332.1434,
found: 332.1448.
Embodiment 2, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
{[Cp*RhCl2]2(3.1 mg, 1 mol %), and AgOTf (128.5 mg, 0.5 mmol), add in 2.0 mL methanol,
Under argon (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess steam
Dry solvent, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 96%.Data characterization is with embodiment 1.
Embodiment 3, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
{[Cp*RhCl2]2}2(3.1 mg, 1 mol %), and AgOTf (5.1 mg, 0.02 mmol), HOTf (44 μ L, 0.5
Mmol), add in 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter,
Dichloromethane washs, and collects organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin
Salt derivative 3aa.Product is white solid, yield 99%.Data characterization is with embodiment 1.
Embodiment 4, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add in 2.0 mL methanol,
Under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess steam
Dry solvent, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 99%.
Embodiment 5, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(CH3CN)3(OTf)2(3.3 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess
Solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 95%.Data characterization is with embodiment 1.
Embodiment 6, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(CH3CN)3(SbF6)2(4.2 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess
Solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 84%.Data characterization is with embodiment 1.
Embodiment 7, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 1 mol %), NaOTf (86.0 mg, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess
Solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 8%.Data characterization is with embodiment 1.
Embodiment 8, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 0.2 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 4 days after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess steam
Dry solvent, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 99%.Data characterization is with embodiment 1.
Embodiment 9, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 0.01 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 8 days after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess steam
Dry solvent, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 74%.Data characterization is with embodiment 1.
Embodiment 10, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (79 μ L, 0.6 mmol), add in 2.0 mL methanol,
Under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess steam
Dry solvent, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aa.Product is that white is solid
Body, yield 66%.Data characterization is with embodiment 1.
Embodiment 11, the preparation of p-methyl benzenesulfonic acid isoquinolin salt derivative 4aa
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
{[Cp*RhCl2]2(3.1 mg, 1 mol %), AgOTs (5.6 mg, 0.02 mmol), HOTs (86.1 mg, 0.5
Mmol), add in 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter,
Dichloromethane washs, and collects organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin
Salt derivative 4aa.Product is white solid, yield 99%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.79 (d,J= 8.6 Hz, 1H), 9.39 (d,J=
8.2 Hz, 1H), 8.77-8.78 (m, 2H), 8.12-8.16 (m, 3H), 7.45-7.56 (m, 8H), 7.36-
7.39 (m, 3H), 7.27-7.29 (m, 2H), 7.09 (d,J= 7.9 Hz, 2H), 2.28 (s, 3H);13C
NMR (100 MHz, DMSO-d 6 ) δ 20.8, 123.5, 124.6, 124.7, 125.4, 126.0, 126.8,
128.0, 128.2, 128.3, 129.3, 129.9, 130.0, 130.8, 131.0, 131.2, 132.0, 134.1,
134.4, 135.3, 136.8, 137.5, 138.3, 140.0, 143.2, 145.8; HRMS (ESI) calcd. for
C25H18N+[M-OTs]: 332.1434, found: 332.1421.
Embodiment 11, the preparation of p-methyl benzenesulfonic acid isoquinolin salt derivative 4aa
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 1 mol %), HOTs (86.1 mg, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic
Phase solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 4aa.Product is white
Solid, yield 94%.Data characterization is with embodiment 11.
Embodiment 12, the preparation of trifluoroacetic acid isoquinolin salt derivative 5aa
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5 mmol),
Cp*Rh(H2O)3(OTf)2(3.0 mg, 1 mol %), TFA (86.1 mg, 0.5 mmol), add 2.0 mL methanol
In, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic
Phase solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 5aa.Product is white
Solid, yield 75%.
Embodiment 13, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ba
Its synthetic route is as follows：
By 2- (4- aminomethyl phenyl)-pyridine 1b (84.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7 mg,
0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0
In mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, receive
Collection organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 4aa.Product
For white solid, yield 91%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.72 (d,J= 8.3 Hz, 1H), 9.29 (d,J=
8.3 Hz, 1H), 8.68-8.74 (m, 2H), 8.00-8.08 (m, 2H), 7.28-7.52 (m, 11H), 2.52
(s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 21.7, 122.6, 123.2, 124.2, 126.0,
128.2, 128.3, 129.3, 129.9, 130.0, 130.9, 131.3, 132.2, 132.4, 134.4, 135.0,
136.6, 138.4, 139.6, 143.1, 145.1; HRMS (ESI) calcd. for C26H20N+[M-OTf]:
346.1590, found: 346.1589.
Embodiment 14, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ca
Its synthetic route is as follows：
By 2- (3- aminomethyl phenyl)-pyridine 1c (84.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7 mg,
0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0
In mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, receive
Collection organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ca.Product
For white solid, yield 91%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.75 (d,J= 8.6 Hz, 1H), 9.23 (s, 1H),
8.70-8.77 (m, 2H), 8.10-8.11 (m, 1H), 7.94-7.96 (m, 1H), 7.34-7.53 (m, 9H),
7.25-7.27 (m, 2H), 2.72(s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 21.4, 123.4,
124.6, 124.7, 125.2, 126.6, 128.2, 128.3, 129.3, 129.8, 130.0, 130.0, 131.0,
131.3, 134.4, 135.2, 135.7, 136.7, 137.5, 139.6, 141.3, 142.9; HRMS (ESI)
calcd. for C26H20N+[M-OTf]: 346.1590, found: 346.1586.
Embodiment 15, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3da
Its synthetic route is as follows：
By 2- (3,5- 3,5-dimethylphenyl)-pyridine 1d (91.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7
Mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add
In 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filters, and dichloromethane washes
Wash, collect organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative
3da.Product is white solid, yield 99%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.73 (d,J= 8.8 Hz, 1H), 9.13 (s, 1H),
8.59-8.65 (m, 2H), 8.06 (t,J= 7.0 Hz, 1H), 7.78 (s, 1H), 7.39-7.42 (m, 5H),
7.21-7.26 (m, 5H), 2.66 (s, 3H), 1.83 (s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ
21.1, 23.2, 123.7, 124.1, 124.4, 126.1, 127.7, 127.9, 128.3, 129.1, 129.7,
130.4, 131.2, 131.7, 135.2, 136.3, 136.5, 137.9, 138.2, 139.3, 139.7, 140.7,
143.2; HRMS (ESI) calcd. for C27H22N+[M-OTf]: 360.1747, found: 360.1731.
Embodiment 16, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ea
Its synthetic route is as follows：
By 2- (4- methoxyphenyl)-pyridine 1e (92.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7
Mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add
In 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filters, and dichloromethane washes
Wash, collect organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative
3ea.Product is white solid, yield 99%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.60 (d,J= 8.7 Hz, 1H), 9.31 (d,J=
9.3 Hz, 1H), 8.59-8.65 (m, 2H), 7.97 (t,J= 7.0 Hz, 1H), 7.78-7.81 (m, 1H),
7.44-7.52 (m, 5H), 7.31-7.40 (m, 3H), 7.26 (d,J= 7.0 Hz, 2H), 6.76-6.77 (m,
1H), 3.81 (s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 55.9, 107.9, 118.7, 120.2,
122.8, 123.2, 128.3, 128.4, 128.6, 129.3, 129.8, 130.0, 130.9, 131.3, 134.3,
134.6, 136.2, 138.8, 139.3, 142.9, 163.2; HRMS (ESI) calcd. for C26H20NO+[M-
OTf]: 362.1526, found: 362.1526.
Embodiment 17, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3fa
Its synthetic route is as follows：
By 2- (3- trifluoromethyl)-pyridine 1f (119.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7
Mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add
In 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filters, and dichloromethane washes
Wash, collect organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative
3fa.Product is white solid, yield 97%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.78 (d,J= 8.7 Hz, 1H), 9.54 (d,J=
9.3 Hz, 1H), 8.79-8.81 (m, 2H), 8.16-8.18 (m, 2H), 7.47-7.50 (m, 5H), 7.38-
7.40 (m, 3H), 7.23-7.28 (m, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 116.4, 119.0,
122.2, 123.4, 125.2, 126.9, 128.4, 128.5, 128.6, 129.3, 129.8, 130.2, 130.5,
130.8, 130.9, 133.7, 133.9, 134.4, 134.6, 136.5, 136.7, 137.2, 139.6, 140.4,
142.7, 148.1, 151.4;19F NMR (376 MHz, DMSO-d 6 ) δ -56.60, -77.57; HRMS (ESI)
calcd. for C26H17F3NO+[M-OTf]: 416.1257, found: 416.1238.
Embodiment 18, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ga
Its synthetic route is as follows：
By 2- (4- fluorophenyl)-pyridine 1g (86.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7 mg,
0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0
In mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, receive
Collection organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ga.Product
For white solid, yield 99%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.74 (d,J= 8.6 Hz, 1H), 9.51 (dd,J 1=
5.0 Hz,J 2= 9.1 Hz, 1H), 8.73-8.79 (m, 2H), 8.08-8.14 (m, 2H), 7.46-7.54 (m,
5H), 7.35-7.41 (m, 3H), 7.28 (d,J= 7.0 Hz, 2H), 7.09-7.11 (m, 1H);13C NMR
(100 MHz, DMSO-d 6 ) δ 111.4, 111.6, 119.0, 119.8, 120.1 ,121.7, 122.2, 123.5,
124.6, 128.5, 129.3, 129.8, 130.0, 130.1, 130.2, 130.8, 131.0, 133.9, 134.6,
134.7, 136.9, 139.4, 140.3, 142.9, 163.3, 165.9;19F NMR (376 MHz, DMSO-d 6 ) δ
-78.19, -102.27; HRMS (ESI) calcd. for C25H17FN+[M-OTf]: 350.1340, found:
350.1325.
Embodiment 19, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ha
Its synthetic route is as follows：
By 2- (3- fluorophenyl)-pyridine 1h (86.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7 mg,
0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0
In mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, receive
Collection organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ha+
3ha’.Product is white solid, yield 71%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.73-9.80 (m, 1.0H), 9.30 (d,J= 13.3
Hz, 0.09H), 9.25 (d,J= 8.5 Hz, 0.91H), 8.72-8.79 (m, 2.01H), 8.14-8.21 (m,
1.96H), 7.88-7.93 (m, 0.98H), 7.45 (s, 5.02H), 7.24 (s, 4.99);13C NMR (100
MHz, DMSO-d 6 ) δ 1119.0, 120.5, 120.7, 120.9, 121.0, 122.2, 122.5, 124.0,
125.4, 126.6, 127.5, 128.4, 128.9, 128.9, 129.2, 129.8, 123.0, 130.8, 131.0,
131.3, 132.0, 132.1, 136.8, 136.8, 137.2, 139.7, 140.7, 142.6, 156.6, 159.2;19F NMR (376 MHz, DMSO-d 6 ) δ -73.04, -100.83, -107.26; HRMS (ESI) calcd. for
C25H17FN+[M-OTf]: 350.1340, found: 350.1349.
Embodiment 20, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ia
Its synthetic route is as follows：
By 2- methylquinoline 1i (84.6 mg, 0.5 mmol), 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ia.Product is
White solid, yield 91%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.63 (d,J= 8.3 Hz, 1H), 9.28 (d,J=
8.3 Hz, 1H), 8.66-8.70 (m, 1H), 8.00-8.11 (m, 3H), 7.40-7.46 (m, 4H), 7.23-
7.33 (m, 5H), 7.18-7.20 (m, 2H), 2.12 (s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ
26.2, 121.5, 125.5, 125.9, 126.9, 128.0, 128.3, 128.3, 128.8, 129.1, 130.0,
130.4, 130.8, 131.6, 133.9, 134.2, 135.6, 137.0, 137.6, 140.1, 147.1, 150.8;
HRMS (ESI) calcd. for C26H20N+[M-OTf]: 346.1590, found: 346.1576.
Embodiment 21, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ja
Its synthetic route is as follows：
By 2- phenylchinoline 1j (102.6 mg, 0.5 mmol), and 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ja.Product is
Faint yellow solid, yield 80%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.55 (d,J= 9.1 Hz, 1H), 9.41 (d,J=
8.6 Hz, 1H), 9.18 (d,J= 9.0 Hz, 1H), 8.39 (d,J= 8.0 Hz, 1H), 8.16-8.18
(m, 2H), 7.98 (d,J= 9.0 Hz, 1H), 7.78 (t,J= 7.4 Hz, 1H), 7.60-7.62 (m,
1H), 7.43-7.51 (m, 4H), 7.16-7.26 (m, 7H);13C NMR (100 MHz, DMSO-d 6 ) δ
119.1, 122.2, 125.2, 125.3, 126.9, 127.3, 128.2, 128.3, 128.4, 128.4, 128.7,
129.2, 130.0, 130.2, 130.5, 131.0, 134.0, 134.4, 135.7, 136.5, 136.6, 136.7,
140.4, 141.1, 148.1; HRMS (ESI) calcd. for C29H20N+[M-OTf]: 382.1590, found:
382.1601.
Embodiment 22, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ka
Its synthetic route is as follows：
By 2- (4- aminomethyl phenyl) quinoline 1k (109.7 mol %), and 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ka.Product is
Faint yellow solid, yield 99%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.48 (d,J= 9.1 Hz, 1H), 9.31 (d,J=
8.6 Hz, 1H), 9.12 (d,J= 9.0 Hz, 1H), 8.37 (d,J= 7.7 Hz, 1H), 8.04 (d,J=
8.5 Hz, 1H), 7.95 (d,J= 8.9 Hz, 1H), 7.76 (t,J= 7.3 Hz, 1H), 7.39-7.49
(m, 5H), 7.16-7.25 (m, 7H), 2.54 (s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 22.0,
118.9, 123.3, 125.3, 126.0, 127.3, 128.2, 128.2, 128.4, 128.7, 128.9, 129.1,
129.8, 130.2, 130.5, 132.8, 134.3, 134.4, 136.3, 136.4, 136.6, 140.5, 140.7,
147.2, 147.8; HRMS (ESI) calcd. for C30H22N+[M-OTf]: 396.1747, found:
396.1754.
Embodiment 23, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3la
Its synthetic route is as follows：
By 2- (4- bromophenyl) quinoline 1l (142.1mg, 0.5mmol), and 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3la.Product is
Faint yellow solid, yield 99%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.55 (d,J= 9.1 Hz, 1H), 9.35 (d,J=
9.1 Hz, 1H), 9.22 (d,J= 9.0 Hz, 1H), 8.40 (t,J= 9.2 Hz, 2H), 7.98 (d,J=
9.0 Hz, 1H), 7.80 (d,J= 7.4 Hz, 1H), 7.65 (s, 1H), 7.46-7.54 (m, 4H), 7.15-
7.27 (m, 7H);13C NMR (100 MHz, DMSO-d 6 ) δ 119.1, 124.4, 125.3, 128.3, 128.6,
128.6,128.7, 128.7, 129.0, 129.3, 129.4, 129.5, 130.2, 130.4, 133.8,134.0,
135.3, 135.4, 136.4, 136.5, 141.6, 148.1; HRMS (ESI) calcd. for C29H19BrN+[M-
OTf]: 460.0695, found: 460.0696.
Embodiment 23, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ma
Its synthetic route is as follows：
By benzo [H] quinoline 1m (90.1mg, 0.5mmol), and 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ma.Product is
Faint yellow solid, yield 87%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.47 (d,J= 7.7 Hz, 1H), 9.22 (d,J=
6.6 Hz, 1H), 8.83 (d,J= 7.6 Hz, 1H), 8.77 (d,J= 9.0 Hz, 1H), 8.67 (d,J=
9.0 Hz, 1H), 8.49-8.54 (m, 2H), 7.86 (d,J= 7.6 Hz, 1H), 7.52-7.62 (m, 5H),
7.36-7.44 (m, 5H);13C NMR (100 MHz, DMSO-d 6 ) δ 118.4, 123.1, 125.3, 126.6,
128.4, 128.5, 128.8, 129.1, 129.5, 129.9, 130.2, 130.2, 130.6, 131.0, 131.1,
132.6, 132.7, 133.3, 134.4, 135.8, 136.4, 138.8, 140.0; HRMS (ESI) calcd. for
C27H18N+[M-OTf]: 356.1434, found: 356.1440.
Embodiment 24, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3na
Its synthetic route is as follows：
By 6- bromobenzene simultaneously [H] quinoline 1n (129.6 mg, 0.5mmol), and 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3na.Product is
Faint yellow solid, yield 71%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.61 (d,J= 7.9 Hz, 1H), 9.36 (d,J=
6.5 Hz, 1H), 9.32 (s, 1H), 8.82 (d,J= 7.6 Hz, 1H), 8.62 (d,J 1= 6.8 Hz,J 2= 8.2 Hz, 1H), 8.56 (t,J= 7.9 Hz, 1H), 7.93 (d,J= 7.4 Hz, 1H), 7.51-
7.60 (m, 5H), 7.39-7.47 (m, 3H), 7.35-7.38 (m, 2H);13C NMR (100 MHz, DMSO-d 6 ) δ 117.7, 119.3, 123.7, 126.0, 127.5, 128.5, 128.9, 129.6, 129.9, 130.3,
130.4, 130.9, 131.1, 132.4, 133.3, 134.1, 136.0, 137.4, 139.2, 139.5; HRMS
(ESI) calcd. for C27H17BrN+[M-OTf]: 434.0539, found: 434.0533.
Embodiment 25, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3oa
Its synthetic route is as follows：
By 1- phenyl -1H- pyrazoles 1o (72.1 mg, 0.5mmol), and 1,2- tolan 2a (89.7 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3oa.Product is
Faint yellow solid, yield 94%.
1H NMR (400 MHz, DMSO-d 6 ) δ 10.03 (d,J= 3.0 Hz, 1H), 8.72 (d,J=
8.4 Hz, 1H), 8.34 (d,J= 3.0 Hz, 1H), 7.97 -8.01 (m, 1H), 7.74 (d,J= 7.7
Hz, 1H), 7.60 (t,J= 3.2 Hz, 1H), 7.48-7.54 (m, 5H), 7.34-7.42 (m, 3H),
7.28-7.33 (m, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 110.7, 115.9, 119.0, 121.9,
122.2, 125.6, 127.3, 128.2, 128.5, 129.2, 129.3, 129.4, 129.6, 130.3, 130.4,
130.5, 131.3, 131.7, 132.3; HRMS (ESI) calcd. for C23H17N2 +[M-OTf]: 321.1386,
found: 321.1396.
Embodiment 26, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3pa
Its synthetic route is as follows：
By (E)-N- benzyl subunit -1- phenylmethanamine 1p (97.6 mg, 0.5mmol), 1,2- tolan 2a (89.7
Mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add
In 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filters, and dichloromethane washes
Wash, collect organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative
3pa.Product is white solid, yield 65%.
1H NMR (400 MHz, CDCl3) δ 10.30 (s, 1H), 8.72 (d,J= 8.0 Hz, 1H),
8.03 (t,J= 7.1 Hz, 1H), 7.97 (t,J= 7.1 Hz, 1H), 7.66 (d,J= 8.3 Hz, 1H),
7.33-7.38 (m, 5H), 7.23-7.26 (m, 2H), 7.08-7.11 (m, 4H), 6.93 (d,J= 7.0 Hz,
2H), 6.83-6.86 (m, 2H), 5.89 (s, 2H);13C NMR (100 MHz, CDCl3) δ 63.2, 125.2,
126.3, 126.5, 127.3, 128.3, 128.4, 128.6, 128.7, 129.2, 129.3, 130.0, 130.1,
130.6, 130.6, 131.2, 131.4, 131.8, 133.0, 137.4, 138.1, 139.8, 140.6, 144.2,
151.3; HRMS (ESI) calcd. for C28H22N+[M-OTf]: 372.1747, found: 372.1747.
Embodiment 27, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3qa
Its synthetic route is as follows：
By (E)-N- (4- methyl benzyl subunit) -1- phenylmethanamine 1q (97.6 mg, 0.5mmol), 1,2- tolan
2a (89.7 mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μL, 0.5
Mmol), add in 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter,
Dichloromethane washs, and collects organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin
Salt derivative 3qa.Product is white solid, yield 70%.
1H NMR (400 MHz, CDCl3) δ 10.20 (s, 1H), 8.59 (d,J= 8.5 Hz, 1H),
7.78 (m, 1H), 7.37 (s, 1H), 7.24-7.31 (m, 3H), 7.21-7.23 (m, 4H), 7.05-7.10
(m, 4H), 6.89-6.91 (m, 2H), 6.83-6.84 (m, 2H), 5.83 (s, 2H), 2.55 (s, 3H);13C
NMR (100 MHz, DMSO-d 6 ) δ 22.6, 62.0, 124.5, 125.2, 127.4, 128.0, 128.2,
128.4, 128.5, 128.7, 128.8, 129.6, 130.1, 130.5, 130.8, 133.3, 133.5, 134.0,
137.8, 138.0, 144.2, 149.7, 150.4; HRMS (ESI) calcd. for C29H24N+[M-OTf]:
386.1903, found: 386.1891.
Embodiment 28, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ra
Its synthetic route is as follows：
By (E)-N- (4- benzyl chloride subunit) -1- phenylmethanamine 1r (97.6 mg, 0.5mmol), 1,2- tolan 2a
(89.7 mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(5.9 mg, 2 mol %), HOTf (44 μL, 0.5
Mmol), add in 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter,
Dichloromethane washs, and collects organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin
Salt derivative 3ra.Product is white solid, yield 79%.
1H NMR (400 MHz, CDCl3) δ 10.30 (s, 1H), 8.68 (d,J= 8.8 Hz, 1H),
7.84 (dd,J 1= 1.6 Hz,J 2= 8.8 Hz, 1H),, 7.58 (d,J= 1.6 Hz, 1H), 7.26-
7.34 (m, 4H), 7.21-7.24 (m, 3H), 7.07-7.10 (m, 4H), 6.89 (d,J= 7.1 Hz, 2H),
6.82-6.85 (m, 2H), 5.83 (s, 2H);13C NMR (100 MHz, DMSO-d 6 ) δ 62.4, 119.0,
124.5, 125.4, 127.5, 128.1, 128.3, 128.5, 128.6, 128.8, 129.8, 130.0, 130.3,
130.5, 131.9, 132.8, 133.4, 133.6, 133.9, 138.1, 138.5, 143.0, 145.2, 151.2;
HRMS (ESI) calcd. for C28H21ClN+[M-OTf]: 406.1357, found: 406.1351.
Embodiment 29, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ab
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), 1,2- bis- (4- methylbenzene) acetylene 2b (103.1 mg,
0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0
In mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, receive
Collection organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ab.Product
For white solid, yield 73%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.75 (d,J= 8.7 Hz, 1H), 9.36 (d,J=
8.3 Hz, 1H), 8.70-8.74 (m, 2H), 8.06-8.16 (m, 3H), 7.49-7.58 (m, 1H), 7.41
(d,J= 8.0 Hz, 2H), 7.30-7.33 (m, 2H), 7.15-7.23 (m, 4H), 2.34 (s, 3H), 2.31
(s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 20.8, 21.0, 123.4, 124.5, 124.6, 125.9,
126.8, 128.4, 129.0, 129.8, 130.0, 130.7, 131.5 132.3, 134.1, 135.3, 136.8,
137.5, 138.4, 139.5, 139.8, 143.2; HRMS (ESI) calcd. for C27H22N+[M-OTf]:
360.1747, found: 360.1748.
Embodiment 30, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ac
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), 1,2- bis- (4- methoxybenzene) acetylene 2c (119.1 mg,
0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0
In mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, receive
Collection organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ac.Product
For white solid, yield 80%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.75 (d,J= 8.7 Hz, 1H), 9.36 (d,J=
8.2 Hz, 1H), 8.82 (d,J= 6.9 Hz, 1H), 8.72 (d,J= 7.9 Hz, 1H), 8.07-8.16
(m, 3H), 7.56 (d,J= 7.9 Hz, 1H), 7.45 (d,J= 8.5 Hz, 2H), 7.20 (d,J= 8.5
Hz, 2H), 7.08 (d,J= 8.6 Hz, 2H), 6.97 (d,J= 8.5 Hz, 2H), 3.80 (s, 3H),
3.77 (s, 3H);13C NMR (100 MHz, DMSO-d 6 ) δ 55.1, 55.2, 113.8, 114.8, 119.0,
123.3, 124.5, 124.6, 125.8, 126.6, 126.9, 130.6, 131.2, 132.4, 132.5, 134.0,
135.4, 136.8, 138.6, 139.7, 143.2, 158.7, 156.0; HRMS (ESI) calcd. for
C27H22NO2 +[M-OTf]: 392.1645, found: 392.1657.
Embodiment 31, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ad
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), and 1,2- bis- (4- fluorobenzene) acetylene 2d (107.1 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ad.Product is
White solid, yield 90%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.79 (d,J= 8.6 Hz, 1H), 9.39 (d,J=
8.3 Hz, 1H), 8.85 (d,J= 6.8 Hz, 1H), 8.76 (t,J= 7.9 Hz, 1H), 8.20-8.10
(m, 3H), 7.53-7.61 (m, 3H), 7.37-7.41 (m, 2H), 7.25-7.34 (m, 4H);13C NMR (100
MHz, DMSO-d 6 ) δ 115.4, 115.6, 116.5, 116.7, 123.4, 124.6, 124.8, 126.0,
126.8, 127.6, 130.6, 131.0, 132.0, 132.1, 132.1, 133.5, 133.6, 134.3, 134.8,
137.2, 137.7, 140.2, 143.2, 160.4;19F NMR (376 MHz, DMSO-d 6 ) δ -77.32, -
109.83, -112.62; HRMS (ESI) calcd. for Chemical Formula: C25H16F2N+[M-OTf]:
368.1245, found: 368.1260.
Embodiment 32, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ae
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), and 1,2- bis- (4- bromobenzene) acetylene 2e (168.0 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ae.Product is
White solid, yield 49%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.78 (d,J= 8.5 Hz, 1H), 9.39 (d,J=
8.3 Hz, 1H), 8.84 (d,J= 6.7 Hz, 1H), 8.76 (t,J= 7.9 Hz, 1H), 8.18 (t,J=
7.2 Hz, 1H), 8.11 (t,J= 7.6 Hz, 2H), 7.77 (d,J= 8.4 Hz, 2H), 7.65 (d,J=
8.4 Hz, 2H), 7.50 (d,J= 9.4 Hz, 3H), 7.23 (d,J= 8.4 Hz, 2H);13C NMR (100
MHz, DMSO-d 6 ) δ 122.0, 123.4, 124.0, 124.6, 124.9, 126.0, 126.8, 130.3,
131.0, 131.5, 131.6, 132.0, 132.6, 133.1, 133.5, 134.3, 137.3, 140.3, 143.2;
HRMS (ESI) calcd. for C25H16Br2N+[M-OTf]: 489.9642, found: 489.9643.
Embodiment 33, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3af
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), and 1- (4- aminomethyl phenyl) phenylacetylene 2f (96.1 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3af+3af '
(1.1:1).Product is white solid, yield 92%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.76 (d,J= 8.8 Hz, 1H), 9.37 (d,J=
8.8 Hz, 1.01H), 8.72-8.77 (m, 2.05H), 8.07-8.16 (3.10), 7.49-7.54 (m, 3.89),
7.35-7.37 (m, 2.65), 7.32-7.34 (m, 2.21), 7.27-7.30 (2.12H), 2.33 (s, 1.58),
2.30 (s, 1.36);13C NMR (100 MHz, DMSO-d 6 ) δ 20.8, 20.9, 123.4, 124.5, 124.6,
124.7, 125.9, 126.8, 126.9, 128.3, 128.3, 128.9, 129.4, 129.8, 129.8, 129.9,
130.1, 130.8, 130.8, 130.9, 131.3, 131.4, 132.1, 132.2, 134.1, 134.5, 135.3,
135.4, 136.8, 137.5, 138.3, 138.4, 139.6, 139.9, 139.9; HRMS (ESI) calcd. for
C26H20N+[M-OTf]: 346.1590, found: 346.1598.
Embodiment 34, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ag
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), 1- (3,5- bis- trifluoromethyl) phenylacetylene 2g
(157.1 mg, 0.5 mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μL, 0.5
Mmol), add in 2.0 mL methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter,
Dichloromethane washs, and collects organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin
Salt derivative 3ag+3ag ' (1.2:1).Product is white solid, yield 97%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.83 (t,J= 8.4 Hz, 1 H), 9.43 (dd,J 1=
3.3 Hz,J 2= 8.2 Hz, 1H), 9.04 (d,J= 6.8 Hz, 0.56H), 8.89 (d,J= 6.8 Hz,
0.46H), 8.81 (dd,J 1= 8.0 Hz,J 2= 15.9 Hz, 1H), 8.31 (s, 1.23H), 8.25-8.12
(m, 4.19H), 8.02 (s, 0.93H), 7.48-7.61 (m, 3.46), 7.34-7.42 (m, 1.79), 7.23-
7.25 (m, 1.15);13C NMR (100 MHz, DMSO-d 6 ) δ 119.0, 121.5, 122.2, 122.3,
123.4, 123.6, 123.9, 124.3, 124.3, 124.6, 124.7, 124.9, 125.1, 126.1,126.2,
126.7, 127.0, 128.5, 128.6, 129.5, 129.7, 130.2, 130.5, 130.9, 131.0, 131.2,
131.2, 131.4, 131.5, 131.7, 132.6, 132.9, 133.7, 133.8, 134.4, 134.7, 135.5,
136.2, 137.2, 138.1, 138.8, 140.4, 140.7, 142.9, 143.3;19F NMR (376 MHz,
DMSO-d 6 ) δ -61.09, -61.16, -77.40; HRMS (ESI) calcd. for C27H16F6N+[M-OTf]:
468.1181, found: 468.1191.
Embodiment 35, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ah
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), phenyl-allylene 2h (58.1 mg, 0.5 mmol), Cp*Rh
(H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add in 2.0 mL methanol, oxygen
Under (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect organic faciess be evaporated molten
Agent, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ah+3ah ' (6:1).Product is
White solid, yield 77%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.72 (d,J= 8.7 Hz, 0.10H), 9.66 (d,J=
8.6 Hz, 0.91H), 9.61 (d,J= 6.9 Hz, 0.09H), 9.30 (d,J= 8.3 Hz, 1.00H),
8.75-8.79 (m, 0.16H), 8.62-8.67 (m, 1.92H), 8.44 (d,J= 8.1 Hz, 0.96H),
8.33-8.37 (m, 0.17H), 8.24 (t,J= 7.8 Hz, 1.00H), 8.15 (t,J= 7.44 Hz,
1.01H), 8.07 (t,J= 7.0 Hz, 1.11H), 7.76-7.83 (m, 2.98H ), 7.69-7.70 (m,
0.27H), 7.63-7.65 (m, 1.91H), 7.42-7.47 (m, 0.24H), 2.74 (s, 0.27H), 2.46 (s,
2.77H);13C NMR (100 MHz, DMSO-d 6 ) δ 16.8, 18.6, 123.3, 123.5, 124.2, 124.4,
125.4, 126.0, 127.0, 128.9, 129.3, 129.6, 130.0, 130.3, 130.4, 130.7, 130.7,
131.6, 131.8, 134.1, 135.3, 136.7, 137.4, 139.1, 139.6, 142.7; HRMS (ESI)
calcd. for C20H16N+[M-OTf]: 270.1277, found: 270.1280.
Embodiment 36, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3ai
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), and 1,3- hexichol -1- propine 2i (96.1 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3ai+3ai '
(6:1).Product is white solid, yield 79%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.70-9.72 (m, 0.93H), 9.26-9.36 (m,
0.99H), 8.79-8.81 (m, 0.27H), 8.67-8.71 (m, 1.73H), 8.19-8.28 (m, 0.67H),
8.07-8.13 (m, 3.88H), 7.57-7.72 (m, 4.54H), 7.48-7.50 (m, 1.3H), 7.15-7.25
(m, 4.65H), 4.29 (s, 1.82H);13C NMR (100 MHz, DMSO-d 6 ) δ 35.2, 123.3, 124.4,
124.9, 126.1, 126.4, 128.0, 128.5, 129.1, 130.1, 130.2, 130.6, 130.8, 131.0,
131.4, 133.9, 137.2, 138.4, 139.2, 139.6, 143.3; HRMS (ESI) calcd. for C26H20N+
[M-OTf]: 346.1590, found: 346.1594.
Embodiment 37, the preparation of trifluoromethanesulfonic acid isoquinolin salt derivative 3aj
Its synthetic route is as follows：
By 2- phenylpyridine 1a (71 μ L, 0.5mmol), and 1,3- hexichol -1- propine 2j (69.1 mg, 0.5
Mmol), Cp*Rh (H2O)3(OTf)2(3.0 mg, 1 mol %), HOTf (44 μ L, 0.5 mmol), add 2.0 mL
In methanol, under oxygen (1atm), 120oC react 22 hours after stopped reaction, kieselguhr filter, dichloromethane wash, collect
Organic faciess solvent evaporated, methanol/ether/petroleum ether（1:4:100）Washing, obtains sterling isoquinolin salt derivative 3aj.Product is
White solid, yield 78%.
1H NMR (400 MHz, DMSO-d 6 ) δ 9.61 (d,J= 7.8 Hz, 1H), 9.55 (d,J=
7.0 Hz, 1H), 9.21 (d,J= 8.3 Hz, 1H), 8.64 (t,J= 7.8 Hz, 1H), 8.42 (d,J=
8.3 Hz, 1H), 8.24 (td,J 1= 1.22 Hz,J 2= 7.1 Hz, 1H), 8.18 (t,J= 7.7 Hz,
1H), 8.06 (t,J= 7.7 Hz, 1H), 3.41-3.45 (m, 2H), 3.25-3.28 (m, 2H), 1.15-
1.23 (m, 8H), 1.00-1.03 (m, 6H);13C NMR (100 MHz, DMSO-d 6 ) δ 13.6, 13.7,
22.0, 22.3, 28.1, 28.3, 28.4, 31.8, 123.7, 124.0, 124.6, 124.9, 126.1, 130.0,
130.9, 132.8, 134.0, 135.6, 138.4, 138.7, 142.7; HRMS (ESI) calcd. for C21H26N+
[M-OTf]: 292.2060, found: 292.2059.
Claims (8)
1. a kind of method of the compound preparing isoquinoline-containing salt structure, methods described course of reaction shown according to the following formula utilizes
Aromatic hydrocarbons, alkynes and acid are raw material, and in the presence of oxidant, transition-metal catalyst catalysis is lower in organic solvent reacts, and is contained
The compound of isoquinoline structure：
Wherein：R1、R2And R3It is each independently selected from following groups：Hydrogen, straight or branched C1-4Alkyl, or C6～C20Aromatic radical
Group, straight or branched C1-4Alkoxyl, halogen, furyl, pyridine radicals, hydroxyl, nitro, amino, straight or branched C1-6Ester group, directly
Chain or side chain C1～C6Acyl group or sulfonic group；Described X is C or N.
2. preparation method according to claim 1 is it is characterised in that R1、R2And R3Be each independently selected from methyl, ethyl,
Propyl group, isopropyl, butyl or isobutyl group.
3. preparation method according to claim 1 is it is characterised in that R1、R2And R3It is each independently selected from methoxyl group, ethoxy
Base, propoxyl group or butoxy.
4. preparation method according to claim 1 is it is characterised in that R1、R2And R3It is each independently selected from phenyl, benzyl,
1- naphthyl or 2- naphthyl.
5. the preparation method according to any one of claim 1-4 is it is characterised in that described transition-metal catalyst is selected from
One of the following or multiple：Rhodium chloride, trichlorine double (4- isopropyl methyl phenyl) rhodium, rhodium acetate, tri-chlorination two（Triphenyl
Phosphorus）Rhodium, tri-chlorination two（Cyclopentadiene）Rhodium, tri-chlorination two（Pentamethylcyclopentadiene）Rhodium, ten dicarbapentaborane four rhodium, three triphenylphosphines
Carbonyl hydrogenation Rh, acetylacetonatodicarrhodium rhodium, vinylimidazolium chloride rhodium, trifluoromethanesulfonic acidization three water（Cyclopentadiene）Rhodium,
Trifluoromethanesulfonic acidization three acetonitrile（Cyclopentadiene）Rhodium, hexafluoro-antimonic acidization three acetonitrile（Cyclopentadiene）Rhodium.
6. the preparation method according to any one of claim 1-4 it is characterised in that described acid be selected from following in one
Plant or multiple：Hydrochloric acid, sulphuric acid, nitric acid, perchloric acid, acetic acid and anhydride, trifluoroacetic acid and anhydride, benzoic acid and its derivants, to first
Benzenesulfonic acid and derivant, trifluoromethanesulfonic acid.
7. the preparation method according to any one of claim 1-4 is it is characterised in that described oxidant is in following
One or more：The tertiary butyl ether of peroxide, tert-Butanol peroxide, hydrogen peroxide, peracetic acid, metachloroperbenzoic acid, peroxidating two are different
Propyl benzene, benzoyl peroxide, Schweinfurt green, silver acetate, silver trifluoroacetate, silver trifluoromethanesulfonate, copper trifluoromethanesulfcomposite, to toluene sulphur
Sour copper, p-methyl benzenesulfonic acid silver, oxygen.
8. the preparation method according to any one of claim 1-4 is it is characterised in that described organic solvent is selected from：Benzene,
Nitromethane, toluene, benzotrifluoride, dimethylbenzene, sym-trimethylbenzene., 1,4- dioxane, acetonitrile, propionitrile, dichloromethane, chloroform,
Carbon tetrachloride, 1,2- dichloroethanes, ether, glycol dimethyl ether, methyl tertiary butyl ether(MTBE), methylcyclopentyl ether, oxolane,N ,N -Dimethylformamide,N ,N- dimethyl acetylamide, dimethyl sulfoxide, methanol, ethanol, tertriary amylo alcohol, or their mixing
Thing.
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