CN113185555B - Pincer-shaped manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application - Google Patents

Pincer-shaped manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application Download PDF

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CN113185555B
CN113185555B CN202110478720.9A CN202110478720A CN113185555B CN 113185555 B CN113185555 B CN 113185555B CN 202110478720 A CN202110478720 A CN 202110478720A CN 113185555 B CN113185555 B CN 113185555B
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王征
刘笑颖
李立斌
马宁
韩鹏
杜兰星
张新颖
吕世松
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Hebei Agricultural University
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Abstract

The invention discloses a pincerlike manganese complex, a preparation method thereof, a prepared ligand, a preparation method thereof, a catalyst composition using the complex as an active component and an application thereof. The catalyst composition taking the pincerlike manganese complex as an active ingredient has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of catalyzing o-amino aryl alcohol or gamma-amino alcohol, ketone or secondary alcohol to perform dehydrogenation coupling reaction to prepare quinoline or pyridine derivatives, and has the advantages of low cost, stable performance, simple operation and high yield.

Description

Pincer-shaped manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
Technical Field
The invention relates to a pincerlike manganese complex, a preparation method thereof, a ligand for preparation, a preparation method thereof, a catalyst composition taking the complex as an active component and application thereof.
Background
Quinoline and pyridine derivatives have important physiological and pharmaceutical activities and have wide requirements in the fields of medicine, agriculture, functional materials, catalytic reaction and the like. Some important drugs (Mini Rev Med Chem 2009,9,1655 j. Med. Chem.2020,63, 10652), such as the antipsychotic drugs Blonanserin (Blonanserin), the ALK inhibitor loratinib (loretinib) and Bosutinib for the treatment of leukemia, all contain pyridine or quinoline building blocks. Thus, a number of classical synthetic methods (Tetrahedron 2004,60,6043-6061, chem. Eur.j.2010,16,12052, chem Rev 2009,109, 2652-2671) were developed for the preparation of quinoline or pyridine derivatives. However, these methods have the disadvantages of harsh reaction conditions (strong acid, strong base, high temperature, etc.), difficulty in obtaining raw materials, complicated steps, low yield, etc.
In recent years, transition metal-catalyzed acceptor-free dehydrocoupling (ADC) reactions have attracted much attention due to their advantages of high atomic utilization, environmental friendliness, and the like. The reaction generally comprises the steps of constructing carbon-carbon bonds and carbon heteroatom bonds through hydrogen transfer or hydrogen strategy, synthesizing complex molecules including pyridine or quinoline in one step, and only producing H as a byproduct 2 And H 2 O, is a sustainable species with practical application valueAnd carrying out green catalytic reaction. For example, rare noble metals [ iridium (angew. Chem. Int. Ed.2017,56,371, j. Org. Chem.2019,84, 6286), ruthenium (chem. Commu. 2013,49,6632, acs cat. 2016,6, 1247), rhodium (j.heterocyclic chem.2005,42, 1219)]And cheap metals [ manganese (ChemCatChem 2020,12,1891]Complexes have been used in the synthesis of quinoline or pyridine derivatives. It is not difficult to find that most of these metal complexes are based on pincer ligands, and most of the inexpensive metal catalysts are mainly focused on the synthesis of quinoline derivatives, with only a few examples for the synthesis of pyridine-type nitrogen heterocycles.
Manganese metal is a metal rich in crust reserves, and a complex catalyst (shown in the following formula) taking manganese as a central metal is rapidly developed in ADC reaction. In 2016, kirchner et al (J.Am.chem.Soc.2016, 138, 15543) treated PN 3 The PMA catalyst was used for the ADC reaction. (o-aminophenyl) (phenyl) methanol and secondary alcohol were converted into 16 cases of quinolines in the presence of 2.1eq.t-BuOK and 0.5eq KOH at 140 ℃ 5 mol%. Srimani et al used NNS manganese catalyst B for the ADC reaction. 1.2eq.t-BuOK as an adjuvant, 140 ℃ C, solvent-free, 5mol% conversion of o-aminoaryl alcohols and secondary alcohols to 15 cases of quinolines. Maji et al (adv. Synth. Catal.2018,360, 3233) by MnBr (CO) 5 Manganese catalyst C was formed in situ with the pyridyl hydrazone tridentate nitrogen ligand for ADC reaction. 0.1eq.t-BuOK is used as an auxiliary agent, tert-amyl alcohol is used as a solvent, and 2mol% of C effectively catalyzes o-aminobenzyl alcohol and acetophenone derivatives to be converted into 10 cases of quinoline compounds at 140 ℃. Madsen et al (chem. Eur.j.2019,25, 6439) used manganese porphyrin catalyst D for the dehydrogenation of anthranilic alcohol with secondary alcohols to quinolines. 2eq.KOH and 2eq.t-BuOK are taken as auxiliary agents,
Figure BDA0003048106460000011
5mol% of O-aminobenzyl alcohol and phenylethanol derivatives in the presence of molecular sieves into 15 examples of 2/2, 3-substituted quinoline nitrogen heterocycles. Srimani et al (org. Lett.2019,21, 3223) used NNS manganese catalyst E for the ADC reaction. 1eq.KOH as adjuvant, 140 ℃,5mol% EBenzyl alcohol and aromatic and aliphatic nitrile are converted into 29 o-quinoline derivatives. When benzonitrile is selected as a substrate, the system can be used for preparing quinazoline. Chen Dafa et al (Organometallics 2019,38, 3218) used a bidentate N-Mn catalyst F for the ADC reaction. 1 eq-BuOK was used as an adjuvant, and O-aminobenzyl alcohol and acetophenone were converted into 9 cases of quinolines at 130 ℃ by 2mol%.
Figure BDA0003048106460000021
Compared with the traditional synthesis method, the research of preparing quinoline or pyridine nitrogen heterocycles by adopting ADC reaction is in the initial stage, and has the following main problems: the activity of the manganese catalyst is low (2.0-5.0 mol%), and the manganese catalyst is not suitable for large-scale industrial production; most of the used high-efficiency catalysts are based on ruthenium and iridium noble metals (0.025-1.0 mol%), and have the defects of potential pollution, toxicity, high production cost and the like; the reaction conditions are harsh, the reaction temperature is higher than 130 ℃, and the use of additives is excessive, so that the industrial application of some processes is limited.
The key point for solving the problems lies in designing a proper ligand, controlling the selectivity of the metal active center to the formation of carbon-carbon bonds and carbon-nitrogen bonds by regulating the electronic effect and the space effect of the ligand, and fundamentally improving the catalytic efficiency and the selectivity of a catalytic system. Therefore, the development of catalysts with higher catalytic activity and cheaper catalysts is a necessary trend in the current development of ADC reactions.
Disclosure of Invention
The invention aims to provide a pincerlike manganese complex which shows excellent catalytic performances of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of catalyzing o-amino aryl alcohol or gamma-amino alcohol, ketone or secondary alcohol to perform dehydrogenation coupling reaction to prepare quinoline or pyridine derivatives.
In order to achieve the purpose, the invention adopts the following technical scheme:
a pincer-like manganese complex comprising a cation complex as follows:
Figure BDA0003048106460000022
wherein Y is NR 1 R 2 、SR 3 Or PR 4 R 5 Said R is 1 Is C 1-6 Alkyl of (b), said R 2 Is C 1-6 Alkyl of (b), said R 3 Is C 1-6 Alkyl, phenyl or C 1-6 Alkyl-substituted phenyl of (a); the R is 4 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a); said R is 5 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a).
Preferably, the pincer-shaped manganese complex has the structure of
Figure BDA0003048106460000031
Said X - Is Br - ，Cl - ，I - Or F - Said R is 1 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; said R is 2 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the R is 3 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, phenyl, methyl-substituted phenyl, ethyl-substituted phenyl or propyl-substituted phenyl; the R is 4 Is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, or propyl-substituted phenyl; the R is 5 Is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, or propyl-substituted phenyl.
Further preferably, X is - Is Br - Y is NMe 2 ，NEt 2 ，N i- Pr 2 SEt, SPh or PPh 2 . Wherein Me represents a methyl group, et represents an ethyl group, i- pr represents an isopropyl group, and the compound has the general formula of, t- bu represents a tert-butyl group.
The invention also aims to provide a preparation method of the pincer-shaped manganese complex, which comprises the step of reacting a compound shown in a formula II with a compound shown in a formula III to obtain a compound shown in a formula I,
Figure BDA0003048106460000032
wherein Y is NR 1 R 2 、SR 3 Or PR 4 R 5 Said R is 1 Is C 1-6 Alkyl of (a), said R 2 Is C 1-6 Alkyl of (b), said R 3 Is C 1-6 Alkyl, phenyl or C 1-6 Alkyl-substituted phenyl of (a); said R is 4 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a); said R is 5 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a). The feeding molar ratio of the compound shown in the formula II to the compound shown in the formula III is 1.0: (0.75 to 2.0), for example, 1.0:0.9. the reaction temperature is 30 to 100 ℃ and, for example, 65 ℃. The reaction time is 12 to 72 hours, for example, 24 hours. The reaction can be carried out in an organic solvent such as ethanol, methanol, tetrahydrofuran, 2-methylfuran, toluene, xylene, etc. The reaction is preferably carried out under an inert gas atmosphere, for example under a nitrogen atmosphere.
The invention also aims to provide a ligand, the structure of which is shown as formula II:
Figure BDA0003048106460000033
wherein Y is NR 1 R 2 、SR 3 Or PR 4 R 5 Said R is 1 Is C 1-6 Alkyl of (a), said R 2 Is C 1-6 Alkyl of (a), said R 3 Is C 1-6 Alkyl, phenyl or C 1-6 Alkyl-substituted phenyl of (a); said R is 4 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a); the R is 5 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a).
Preferably, said R is 1 Is methyl, ethyl, n-propyl, isopropyl, n-butyl or isopropylButyl or tert-butyl; the R is 2 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the R is 3 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, phenyl, methyl-substituted phenyl, ethyl-substituted phenyl or propyl-substituted phenyl; the R is 4 Is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, or propyl-substituted phenyl; the R is 5 Is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, or propyl-substituted phenyl.
The preparation method of the ligand comprises the step of adding a compound shown as a formula IV and a compound shown as a formula V into NaBH (OAc) 3 Carrying out reductive amination reaction in the presence of a catalyst to obtain a compound shown as a formula II;
Figure BDA0003048106460000041
wherein Y is NR 1 R 2 、SR 3 Or PR 4 R 5 Said R is 1 Is C 1-6 Alkyl of (a), said R 2 Is C 1-6 Alkyl of (a), said R 3 Is C 1-6 Alkyl, phenyl or C 1-6 Alkyl-substituted phenyl of (a); the R is 4 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a); the R is 5 Is phenyl or C 1-6 Alkyl-substituted phenyl of (a). The feeding molar ratio of the compound shown in the formula IV to the compound shown in the formula V is 1.0:0.8 to 4.0, for example 1.0:1.2;1.0:2.0, etc. The reaction temperature is 20-80 ℃, for example, 30 ℃; the reaction time is 12 to 48 hours, for example 24 hours; the solvent for the reaction is ethanol, dichloromethane, acetic acid, 1, 2-dichloromethane, tetrahydrofuran, toluene, etc.
The invention also aims to provide a catalyst composition which comprises an active ingredient and an auxiliary agent, wherein the active ingredient is the pincer-shaped manganese complex.
Preferably, the auxiliary agent is t-BuOK, t-BuONa, i-PrONa, etONa, meONa, KOH, naOH, naHBEt 3 、K 2 CO 3 、Na 2 CO 3 One or more of the above.
The last object of the present invention is to provide the application of the pincer-shaped manganese complex or the catalyst composition, wherein the application is to catalyze the o-amino aromatic alcohol or gamma-amino alcohol, ketone or secondary alcohol to perform dehydrogenation coupling reaction to prepare quinoline or pyridine derivatives, and the reaction formula is as follows:
Figure BDA0003048106460000042
Figure BDA0003048106460000051
the R is 9 And R 10 Is H, methyl, ethyl, propyl, butyl, methoxy, ethoxy, F, cl, br, I or Ph; r 8 H, methyl, ethyl, propyl, butyl, methoxy, ethoxy, F, cl, br, I or Ph;
the R is 6 Is methyl, ethyl, propyl, butyl, phenyl, C 1-3 Substituted phenyl, pyridyl, thienyl, furyl, naphthyl; the R is 7 H, methyl, ethyl, propyl, butyl; or R 6 、R 7 Is at both ends of a chain alkyl group of 3 to 20 carbons.
Adding o-amino aryl alcohol or gamma-amino alcohol, ketone or secondary alcohol and the pincerlike manganese complex into a solvent, and reacting for 12-48 h at 110-140 ℃ in an inert gas atmosphere to obtain the quinoline or pyridine derivative. The solvent is toluene and tetrahydrofuran, the volume ratio of the toluene to the tetrahydrofuran is 4, the catalyst composition is a combination of a pincer-shaped manganese complex, KOH and t-BuOK, the molar amount of the pincer-shaped manganese complex is 5.0-0.05% of amino alcohol, and the molar ratio of o-amino aryl alcohol or gamma-amino alcohol, ketone or secondary alcohol, t-BuOK, KOH is 1.
According to the pincerlike manganese complex provided by the invention, a cycloalkyl ring is introduced into a ligand framework, and the reactivity and stability of a manganese metal center can be effectively regulated by regulating the ring tension, flexibility and steric hindrance of the cycloalkyl ring, so that the catalytic activity and substrate applicability of a manganese metal system are obviously improved. The catalyst composition taking the pincerlike manganese complex as an active ingredient has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of catalyzing o-amino aryl alcohol or gamma-amino alcohol, ketone or secondary alcohol to perform dehydrogenation coupling reaction to prepare quinoline or pyridine derivatives, and has the advantages of low cost, stable performance, simple operation and high yield.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of Mn-1.
FIG. 2 is a schematic representation of the crystal structure of Mn-4.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
C 1-6 Alkyl means an alkyl group having 1 to 6 carbons, and includes straight or branched chain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. C 1-3 The substituted phenyl group of (2) includes methyl-substituted phenyl, ethyl-substituted phenyl, n-propyl-substituted phenyl, isopropyl-substituted phenyl and the like. C 1-6 The alkyl-substituted phenyl group of (1) includes methyl-substituted phenyl, ethyl-substituted phenyl, n-propyl-substituted phenyl, isopropyl-substituted phenyl, n-butyl-substituted phenyl, sec-butyl-substituted phenyl, isobutyl-substituted phenyl, tert-butyl-substituted phenyl, pentyl-substituted phenyl, hexyl-substituted phenyl and the like, and also includes cycloalkyl-substituted phenyl having 3 to 6 carbons. Both ends of the chain alkyl group of 3 to 20 carbons include CH at both ends of a straight chain or branched alkyl group of 3,4, 5,6,7,8,9,10,11,12,13,14, 15,16,17,18, 19 or 20 carbons 2 (it may be CH, C, etc. in the middle of the carbon chain).
The process is conventional unless otherwise specified, all operations being carried out under nitrogen using Schlenk's technique, all solvents being distilled before use. The starting materials are commercially available from the open literature unless otherwise specified.
EXAMPLE 1 Compound N of formula II 1 ,N 1 -dimethyl-N 2 - (5,6,7,8-tetrahydroquinolin-8-yl) -1, 2-ethanediamine (L1, Y = NMe) 2 ) Preparation of (2)
Figure BDA0003048106460000061
Under a nitrogen atmosphere, 2.94g (20 mmol) of 6, 7-dihydro-5H-quinolin-8-one, 2.12g (24mmol, 1.2eq.) of N, N-dimethylethylenediamine and 6.33g (30mol, 1.5eq.) of sodium triacetoxyborohydride (NaBH (OAc) 3 Placed in a 100mL Schlenk flask followed by 60mL 1, 2-Dichloroethane (DME). After the mixture was stirred at 30 ℃ for 12 hours, the reaction was checked by TLC and saturated NaHCO was added 3 The reaction was quenched with aqueous solution (pH > 8). The mixture was extracted with ethyl acetate (3X 30 mL), the combined organic phases were dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure to give 3.25g of yellow oil L1 in 74% yield.
The structure confirmation data is as follows:
1 H NMR(CDCl 3 ,400MHz)δ8.30(d,J＝4.0Hz,1H),7.30–7.26(m,1H),6.97(dd,J＝7.7,4.7Hz,1H),3.72(d,J＝5.4Hz,1H),3.70(s,1H),2.78–2.61(m,4H),2.42(td,J＝6.4,3.3Hz,2H),2.17(s,6H),2.09–2.00(m,1H),1.95–1.87(m,1H),1.78–1.58(m,2H)； 13 C NMR(CDCl 3 ,100MHz)δ157.36,146.73,136.85,132.39,121.88,59.43,57.85,45.63,45.50,44.99,28.83,28.56,19.53。
EXAMPLE 2 Compound N of formula II 1 ,N 1 -diethyl-N 2 - (5,6,7,8-tetrahydroquinolin-8-yl) -1, 2-ethanediamine (L2, Y = NEt) 2 ) Preparation of (2)
Figure BDA0003048106460000062
Using a similar preparation and molar ratio to L1 in example 1, 3.50g of L2 are obtained as a yellow oil in a yield of 70%.
The structure validation data is as follows:
1 H NMR(CDCl 3 ,400MHz)δ8.30(dd,J＝4.8,1.6Hz,1H),7.30(dd,J＝7.7,1.6Hz,1H),6.99(dd,J＝7.7,4.7Hz,1H),5.18(s,1H,NH),3.78(dd,J＝8.1,5.4Hz,1H),2.82–2.65(m,4H),2.65–2.58(m,2H),2.52(q,J＝7.1Hz,4H),2.16–2.07(m,1H),1.98–1.90(m,1H),1.81–1.60(m,2H),0.97(t,J＝7.1Hz,6H,CH 3 )； 13 C NMR(CDCl 3 ,100MHz)δ156.51,146.77,136.97,132.52,122.00,57.83,52.30,46.88,44.38,28.72,28.18,19.77,11.38。
the crude L2 was further purified by acidification treatment with aqueous HCl (0: 10 ml/10 w%) added to yield 4.85g of the ligand hydrochloride as a pale yellow solid with an overall yield of 68%.
The structure confirmation data is as follows:
1 H NMR(D 2 O,400MHz)δ8.54(d,J＝5.2Hz,1H),8.13(d,J＝7.9Hz,1H),7.71(ddt,J＝7.8,5.1,2.6Hz,1H),4.58(d,J＝5.7Hz,1H),3.64–3.45(m,4H),3.33–3.26(m,4H),3.07–2.87(m,2H),2.30(d,J＝11.8Hz,1H),2.10(s,1H),2.03–1.89(m,2H),1.28(t,J＝7.3Hz,6H)。
example 3 Compound N of formula II 1 ,N 1 -diisopropyl-N 2 - (5,6,7,8-tetrahydroquinolin-8-yl) -1, 2-ethanediamine (L3, Y = N) i- Pr 2 ) Preparation of
Figure BDA0003048106460000071
Using a similar preparation and molar ratio to L1 in example 1, 4.80g of L3 were obtained as a yellow oil in 87% yield.
The structure validation data is as follows:
1 H NMR(400MHz,CDCl 3 )δ8.40(d,J＝4.6Hz,1H),7.37(d,J＝7.6Hz,1H),7.06(dd,J＝7.6,4.8Hz,1H),3.84–3.77(m,1H),3.22(dd,J＝11.3,5.6Hz,1H),3.03(dt,J＝13.1,6.6Hz,2H),2.83-2.72(m,4H),2.69–2.64(m,2H),2.18(dt,J＝10.6,5.3Hz,1H),2.06–1.96(m,1H),1.87–1.70(m,2H),1.04(d,J＝6.6Hz,12H)。
crude L3 was further purified by acidification with addition of 10mL10w% aqueous HCl solution to obtain 6.15g of a pale yellow solid ligand hydrochloride in an overall yield of 80%.
The structure validation data is as follows:
1 H NMR(400MHz,D 2 O)δ8.56(dd,J＝5.6,1.5Hz,1H),8.20(dd,J＝8.2,1.5Hz,1H),7.77(dd,J＝8.1,5.5Hz,1H),4.69(d,J＝4.6Hz,1H),3.73-3.67(m,2H),3.65–3.58(m,1H),3.50(dt,J＝11.2,7.4Hz,1H),3.41(dd,J＝9.0,7.2Hz,2H),3.00(dt,J＝18.2,5.2Hz,1H),2.87(dt,J＝17.9,7.6Hz,1H),2.19(dtt,J＝29.8,9.8,4.8Hz,2H),1.97–1.83(m,2H),1.30–1.21(m,12H)； 13 C NMR(100MHz,DMSO-d 6 )δ157.07,146.93,137.26,132.41,122.46,58.15,47.95,47.02,44.06,28.59,21.58,20.54,19.67。
EXAMPLE 4 preparation of 2- (ethylthio) ethylamine
Figure BDA0003048106460000072
Under a nitrogen atmosphere, 11.3g (0.10 mol) of 2-chloroethylamine hydrochloride, 4.0g (0.10 mol) of NaOH and 4.6g (0.20 mol) of LiOH were placed in a container containing 120mL of EtOH and 30mL of H 2 O in a 250mL single-neck bottle. After the mixture was stirred at 0 ℃ for 10 minutes, 11.8g (110 mmol) of bromoethane was added dropwise to the mixture, maintaining the temperature below 5 ℃. After the addition is finished, slowly heating the system to 35 ℃, continuing stirring for 24 hours, after the reaction is finished by GC detection, filtering to remove a large amount of inorganic salt, and removing a large amount of ethanol from the filtrate by spin drying. To the concentrate was added 40mL of water, and the mixture was extracted with methylene chloride (3X 60 mL). Organic phase organic anhydrous NaSO 4 Drying and concentration under reduced pressure gave 6.5g of 2- (ethylthio) ethylamine as a yellow oil in 61% yield.
The structure validation data is as follows:
1 H NMR(400MHz,DMSO-d 6 )δ2.74(t,J＝7.0Hz,2H),2.58(d,J＝7.3Hz,1H),2.51(dd,J＝9.8,4.9Hz,1H),1.17(t,J＝7.4Hz,4H)。
example 5 preparation of the Compound of formula II N- (2- (ethylsulfanyl) - (5, 6,7, 8-tetrahydroquinolin-8-yl) -1-ethylamine (L4, Y = SEt)
Figure BDA0003048106460000073
Using the starting materials from example 4 and using similar preparation and molar ratios as L1 in example 1, 4.20g of L4 were obtained as a yellow oil in 88% yield.
The structure validation data is as follows:
1 H NMR(400MHz,DMSO-d 6 )δ8.37(dd,J＝4.8,1.6Hz,1H),7.51–7.44(m,1H),7.19–7.13(m,1H),3.67(t,J＝6.2Hz,1H),2.87–2.59(m,6H),2.52(q,J＝7.4Hz,2H),2.10–1.80(m,3H),1.65(ddt,J＝10.3,7.2,4.1Hz,2H),1.19(t,J＝7.4Hz,3H)； 13 C NMR(100MHz,DMSO-d 6 )δ157.82,146.91,137.25,132.35,122.34,57.58,31.82,29.05,28.67,25.39,19.50,15.36。
example 6 preparation of Compound Mn-1 of formula 1
Figure BDA0003048106460000081
Under a nitrogen atmosphere, 219mg (1 mmol) of N 1 ,N 1 -dimethyl-N 2 - (5, 6,7, 8-tetrahydroquinolin-8-yl) -1, 2-ethanediamine (L1) and 275mg (1 mmol) of manganese pentacarbonyl bromide (Mn (CO) 5 Br) was placed in a 25mL Schlenk flask and 10mL of dry THF was added. The mixture was stirred at 65 ℃ for 24 hours. The solvent was concentrated under reduced pressure and the solid residue was washed with 10mL of diethyl ether and dried to give a pale yellow solid. The yellow solid was dissolved in a small amount of dichloro-benzene, and then a large amount of diethyl ether was added to precipitate pale yellow solid Mn-1, which was dried to 375mg, in 85% yield.
The structure validation data is as follows:
1 H NMR(400MHz,DMSO-d 6 )δ8.84(s,1H,NH),7.89(d,J＝7.2Hz,1H),7.61–7.48(m,1H),7.39–7.23(m,1H),4.35(d,J＝9.6Hz,1H),3.05–2.75(m,6H),2.59(d,J＝11.6Hz,1H),2.44-2.42(m,1H),2.14(d,J＝15.6Hz,2H),1.93(s,6H,CH 3 )； 13 C NMR(100MHz,DMSO-d 6 ) δ 219.64,219.26,218.98,158.68,152.46,140.24,136.87,125.81,64.81,62.97,57.00,49.03,43.62,27.42,26.68,21.14; elemental analysis: [ C ] 16 H 21 BrMnN 3 O 3 (Mw:438.20)]:C,43.86；H,4.83；N,9.59；Found:C,43.90；H,4.96；N,9.54；IR(ATR,cm -1 ,KBr):1753(s,v CO ),1779(s,v CO ),1898(s,v CO )。
A schematic diagram of the crystal structure of Mn-1 is shown in FIG. 1.
As can be seen from FIG. 1, the central metal Mn of the complex Mn-1 adopts a six-coordination mode, and is respectively connected with a nitrogen atom N1 on a pyridine ring of a ligand, two nitrogen atoms N2 and N3 on ethylenediamine and three carbonyl carbons C14, C15 and C16 to form a distorted octahedral structure.
Example 7 preparation of Compound Mn-2 of formula 1
Figure BDA0003048106460000082
Using a similar preparation method and molar ratios as Mn-1 in example 6, 412mg of Mn-2 were obtained as a pale yellow powder in a yield of 89%.
1 H NMR(500MHz,DMSO-d 6 )δ8.84(br,1H),7.91(s,1H),7.56(s,1H),7.19(s,1H),4.40(s,1H),3.29(s,4H),2.85(s,4H),2.04–2.00(m,4H),1.43(s,1H),1.30(br,3H),1.16(s,1H),0.91(s,3H)； 13 C NMR(100MHz,DMSO-d 6 ) δ 157.73,149.59,138.32,135.70,123.55,62.77,56.44,53.50,44.57,41.62,28.10,27.04,21.46,9.31,9.20, no signal peak for carbonyl carbon was observed; elemental analysis: [ C ] 18 H 25 BrMnN 3 O 3 (Mw:466.26)]:C,46.37；H,5.40；N,9.01；Found:C,46.46；H,5.51；N,8.92；IR(ATR,cm -1 ,KBr):1755(s,v CO ),1778(s,v CO ),1891(s,v CO )。
Example 8 preparation of Mn-3 Compound represented by formula 1
Figure BDA0003048106460000091
Using a similar preparation and molar ratio as Mn-1 in example 6, 425mg of Mn-3 were obtained as a yellow powder in a yield of 85%.
1 H NMR(500MHz,DMSO-d 6 )δ8.78(br,1H),7.76(d,J＝2.2Hz,1H),7.53–7.37(m,1H),4.31–4.13(m,1H),3.41(d,J＝34.6Hz,1H),3.21(s,1H),2.97(d,J＝6.8Hz,2H),2.93–2.71(m,4H),2.02(s,1H),1.79(s,1H),1.64(s,2H),1.02(s,12H)； 13 C NMR(125MHz,DMSO-d 6 ) Delta 158.02,151.90,139.41,139.15,135.36,134.99,125.16,64.73,53.72,48.33,47.74,43.23, 43.05,28.12,27.26,26.15,22.32,21.59,21.01,20.07, no signal peak of carbonyl is detected; elemental analysis: [ C ] 20 H 29 BrMnN 3 O 3 (Mw:494.31)]:C,48.60；H,5.91；N,8.50；Found:C,48.65；H,5.97；N,8.44；IR(ATR,cm -1 ,KBr):1751(s,v CO ),1785(s,v CO ),1902(s,v CO )。
Example 9 preparation of Mn-4 Compound represented by formula 1
Figure BDA0003048106460000092
Using a similar preparation method and molar ratio as Mn-1 in example 6, 395mg of Mn-4 was obtained as a pale yellow powder in 87% yield.
Diethyl ether was slowly added to a saturated solution of Mn-4 dichloromethane at room temperature to obtain green crystals.
1 H NMR(500MHz,DMSO-d 6 )δ8.65(d,J＝1.5Hz,1H),7.83(d,J＝6.1Hz,1H),7.50(d,J＝4.6Hz,1H),4.38(s,1H),3.15–3.00(m,2H),2.89(d,J＝8.3Hz,1H),2.83–2.60(m,4H),2.09(s,1H),2.04–1.74(m,4H),1.72–1.56(m,1H),1.36-1.19(m,3H)；13C NMR(125MHz,DMSO-d 6 ) δ 217.45 (C = O), 211.06 (C = O), 211.00 (C = O), 159.10,151.69,140.28,135.76,125.97,63.83,46.09,33.02,31.30,27.14,26.19,21.01,13.66; elemental analysis [ C 16 H 20 BrMnSN 2 O 3 (Mw:455.25)]:C,42.21；H,4.43；N,6.15；Found:C,42.23；H,4.51；N,6.08；IR(ATR,cm -1 ,KBr):1917(s,v CO ),1947(s,v CO ),2027(s,v CO )。
The crystal structure of Mn-4 is schematically shown in FIG. 2.
As can be seen from FIG. 2, the central metal Mn of the complex Mn-4 adopts a six-coordination mode, and is respectively connected with a nitrogen atom N1 on a pyridine ring of a ligand, a nitrogen atom N2 on an ethylamine thioether group, a sulfur atom S1 and three carbonyl carbons C14, C15 and C16 to form a distorted octahedral structure.
Example 10 preparation of Mn-5 Compound represented by formula 1
Figure BDA0003048106460000101
Using a similar preparation method and molar ratio as Mn-1 in example 6, 457mg of Mn-5 as pale yellow powder was obtained.
1 H NMR(500MHz,DMSO-d 6 )δ8.15(d,J＝5.3Hz,1H,trans),7.83(d,J＝8.7Hz,1H),7.76(d,J＝6.0Hz,1H),7.63(d,J＝7.1Hz,trans),7.57(d,J＝5.6Hz,3H),7.32(dt,J＝27.0,7.5Hz,5H),7.16(t,J＝9.1Hz,2H),6.81(t,J＝6.5Hz,1H,cis),4.35(s,1H,CNH,cis),3.97(s,CNH,trans),3.76–3.53(m,CH,trans),3.25(t,J＝15.2Hz,CH,cis),3.03–2.73(m,3H),2.73–2.52(m,3H),2.23–1.94(m,2H),1.92–1.50(m,2H). 13 C NMR(125MHz,DMSO-d 6 )δ214.71(CO),214.61(CO),162.63,158.31,151.51,150.25,139.35,138.48,136.00,134.75,133.16,132.80,132.61,132.53,132.10,132.02,131.91,131.83,131.54,131.37,131.24,131.14,131.02,130.96,129.96,129.89,129.80,129.70,129.62,129.49,129.41,129.24,125.37,124.81,64.95 cis ,63.18 trans ,27.29 cis ,26.79 trans ,26.49 cis ,26.29 trans ,25.13 cis ,24.94 cis ,23.76 trans ,23.58 trans ,21.23 cis ,19.69 trans ； 31 P NMR (202MHz, DMSO-d) delta 69.75 (1-trans), 63.99 (1-cis); elemental analysis: [ C ] 26 H 25 PBrMnO 3 N 2 (Mw:579.31)]:C,53.91；H,4.34；N,4.83；Found:C,54.03；H,4.42；N,4.81；IR(ATR,cm -1 ,KBr):1845(s,v CO ),1878(s,v CO ),1927(s,v CO ).
EXAMPLE 11 Compound Mn-4 of formula 1 catalyzes the dehydrocoupling of anthranilic alcohol (1 a) with cycloheptanone (2 a) to 7,8,9, 10-tetrahydro-6H-cyclohepta [ b ] quinoline (3 aa)
At N 2 61mg (0.5 mmol) of o-aminobenzyl alcohol, 112mg (2 eq.,1.0 mmol) of cycloheptanone, 4.5mg (10umol, 2mol%) of Mn-4, 1.0mmol (2 eq.) of a base cocatalyst were put into a 20mL Schlenk bottle under an atmosphere, and a certain amount (2.0 to 4.0 mL) of toluene and (0.5 to 1.0 mL) of tetrahydrofuran were added. The reaction mixture is stirred and reacted for 48 to 72 hours at the temperature of 120 ℃. Cooled to room temperature and 5mL of saturated NH was added 4 The results of GC analysis of the aqueous Cl solution (with mesitylene as an internal standard) are shown in Table I.
Figure BDA0003048106460000102
Table one: results of 3aa preparation by dehydrocoupling reaction with different cocatalysts a 。
Figure BDA0003048106460000103
Figure BDA0003048106460000111
a The reaction conditions are as follows: 0.5mmol of o-aminobenzyl alcohol, 1.0mmol of cycloheptanone, 10umol of Mn-4, 1.0mmol of alkali auxiliary agent, 4.0mL of toluene and 1.0mL of tetrahydrofuran at 120 ℃ for 72h; b the conversion rate and the yield are detected by GC, and mesitylene is used as an internal standard substance; e 2.0mL of toluene and 0.5mL of THF, f 48 hours; g in the absence of Mn-4.
From Table I, t-BuOK, meONa, KOH, naOH or CsCO can be found 3 Mn-4 exhibits a good catalytic activity as a base cocatalyst, among whichWhen potassium tert-butoxide and potassium hydroxide are used as alkali promoters, the reaction is carried out for 48h, the system shows the highest catalytic activity, the conversion rate reaches 99%, and the product yield reaches 97%.
Example 12 Mn-4 Compound of formula 1 Mn-4 catalyzes the conversion of anthranilic alcohol (1 a) and cycloheptanone (2 a) to 3aa under different ratios of t-BuOK to KOH
In N 2 61mg (0.5 mmol) of anthranilic alcohol, 112mg (2 eq.,1.0 mmol) of cycloheptanone, 4.5mg (10umol, 2mol%) of Mn-4, 0.25 to 1.0mmol (0.5 to 2 eq.) of t-BuOK, and 0.25 to 1.0mmol (0.5 to 2 eq.) of KOH were put into a 20mL Schlenk bottle under an atmosphere, and 2.mL of toluene and 0.5mL of tetrahydrofuran were added. The reaction mixture is stirred and reacted for 24 to 48 hours at the temperature of 120 ℃. Cooled to room temperature and 5mL of saturated NH was added 4 The results of GC analysis of the aqueous Cl solution (with mesitylene as an internal standard) are shown in Table II.
Figure BDA0003048106460000112
TABLE results of 3aa preparation by dehydrocoupling reaction at different ratios of di-t-BuOK and KOH a
Figure BDA0003048106460000113
a The reaction conditions are as follows: 0.5mmol of anthranilic alcohol, 1.0mmol of cycloheptanone, 10umol of Mn-4, 2.0mL of toluene and 0.5mL of tetrahydrofuran, at 120 ℃ for 48h; b the conversion rate and the yield are detected by GC, and mesitylene is used as an internal standard substance; c 24 h
example 13 Mn-4 Compound of formula 1 catalyzes the conversion of anthranilic alcohol (1 a) and cycloheptanone (2 a) to 3aa
At N 2 Under protection, 61mg (0.5 mmol) of o-aminobenzyl alcohol, 112mg (2 eq.,1.0 mmol) of cycloheptanone, 4.5mg (10umol, 2mol%) of Mn-4, 117mg (1.0 mmol) of t-BuOK, 56mg (1.0 mmol) of KOH were placed in a 20mL Schlenk bottle, and 2.0mL of toluene and 0.5mL of tetrahydrofuran were added. The reaction mixture was stirred at 120 ℃ for 24 hours. Cooled to room temperature and 5mL of saturated NH was added 4 Dissolving Cl in waterLiquid, GC detection analysis (with mesitylene as internal standard)
Figure BDA0003048106460000114
TABLE III results of the dehydrogenation coupling reaction in different solvents to prepare 3aa a
Figure BDA0003048106460000115
Figure BDA0003048106460000121
a Reaction conditions are as follows: 0.5mmol of o-aminobenzyl alcohol, 1.0mmol of cycloheptanone, 10umol of Mn-4, 1.0mmol of t-BuOK, 1.0mmol of KOH, 2.0mL of toluene and 0.5mL of tetrahydrofuran, at 120 ℃ for 24h under the condition of nitrogen; b conversion and yield were determined by GC using mesitylene as internal standard.
Example 14 Mn-4 Compound of formula 1 catalyzes the conversion of anthranilic alcohol (1 a) to 3aa in different reaction times with cycloheptanone (2 a)
At N 2 Under an atmosphere, 61mg (0.5 mmol) of o-aminobenzyl alcohol, 112mg (2 eq.,1.0 mmol) of cycloheptanone, 4.5mg (10umol, 2mol%) of Mn-4, 117mg (1.0mmol, 2eq.) of t-BuOK, and 56mg (1.0mmol, 2eq.) of KOH were placed in a 20mL Schlenk bottle, and 2.mL of toluene and 0.5mL of tetrahydrofuran were added. The reaction mixture is stirred and reacted for 3 to 48 hours at 120 ℃. Cooled to room temperature and 5mL of saturated NH was added 4 The results of GC analysis of the aqueous Cl solution (with mesitylene as an internal standard) are shown in Table four.
Figure BDA0003048106460000122
TABLE results of 3aa preparation by dehydrocoupling reaction at four different reaction times a
Figure BDA0003048106460000123
a The reaction conditions are as follows: 0.5mmol of anthranilic alcohol, 1.0mmol of cycloheptanone, 10umol of Mn-4, 1.0mmol of t-BuOK, 1.0mmol of KOH, 2.0mL of toluene and 0.5mL of tetrahydrofuran, and the nitrogen condition is carried out at 120 ℃ for 3-48 h; b the conversion and yield were determined by GC with mesitylene as internal standard.
Example 15 catalytic conversion of O-aminobenzyl alcohol (1 a) to 3aa with cycloheptanone (2 a) at different Mn-4 loadings
Under the nitrogen atmosphere, 0.5-2.0 mmol of 2-aminobenzyl alcohol, 1.0-4.0 mmol of cycloheptanone, 1.0-10 mmol of Mn-4, 1.0-4.0 mmol of t-BuOK and 1.0-4.0 mmol of KOH are put into a Schlenk bottle with 20-100 mL, 2.0-8.0 mL of toluene and 0.5-2.0 mL of tetrahydrofuran are added into the solution, and the reaction mixture is stirred and reacted for 24 hours at the temperature of 120 ℃. Cooled to room temperature and 5mL of saturated NH was added 4 The results of GC analysis of the aqueous Cl solution (with mesitylene as an internal standard) are shown in Table five.
Figure BDA0003048106460000124
TABLE five results of dehydrogenation coupling reaction preparation 3aa under different manganese loadings a
Figure BDA0003048106460000131
a Reaction conditions are as follows: 0.5-2.0 mmol of o-aminobenzyl alcohol, 1.0-4.0 mmol of cycloheptanone, 1.0-10 umol of Mn-4, 1.0-4.0 mmol of t-BuOK, 1.0-4.0 mmol of KOH, 2.0-8.0 mL of toluene and 0.5-2.0 mL of tetrahydrofuran, wherein the molar ratio of the substrate to the catalyst is C = 120 ℃; b the conversion and yield were determined by GC with mesitylene as internal standard.
Example 16 Compound Mn-4 of formula 1 catalyzes the conversion of anthranilic alcohol (1 a) and cycloheptanone (2 a) to 3aa at different temperatures
Under a nitrogen atmosphere, 61mg (0.5 mmol) of o-amino groupBenzyl alcohol, 112mg (2 eq.,1.0 mmol) of cycloheptanone, 4.5mg (10umol, 2mol%) of Mn-4, 117mg (1.0 mmol) of t-BuOK, and 56mg (1.0 mmol) of KOH were put in a 20mL Schlenk bottle, 2.0mL of toluene and 0.5mL of tetrahydrofuran were added, and the reaction mixture was stirred at 20 to 120 ℃ for 24 hours. Cooled to room temperature and 5mL of saturated NH was added 4 The results of GC analysis of the aqueous Cl solution (with mesitylene as an internal standard) are shown in Table seven.
Figure BDA0003048106460000132
TABLE results of 3aa preparation by dehydrocoupling reaction at six different temperatures
Figure BDA0003048106460000133
a Reaction conditions are as follows: 0.5mmol of 2-aminobenzyl alcohol, 1.0mmol of cycloheptanone, 1.0mmol of t-BuOK, 1.0mmol of KOH, 5.0umol of Mn-4, 2.0mL of toluene, 0.5mL of tetrahydrofuran, 20-120 ℃ and 24 hours; b the conversion and yield were determined by GC with mesitylene as internal standard.
Example 17 conversion of anthranilic alcohol (1 a) and cycloheptanone (2 a) or cycloheptanol (2 a') to 3aa with the compound represented by formula 1 (Mn-1-Mn-5)
At N 2 Under protection, 121mg (1.0 mmol) of anthranilic alcohol, 224mg (2 eq.,2.0 mmol) of cycloheptanone or 228mg (2 eq.,2.0 mmol) of cycloheptanol, 10umol (1 mol%) of the compound represented by formula 1 (Mn-1-Mn-5), 234mg (1.0 mmol) of t-BuOK, 112mg (1.0 mmol) of KOH are placed in a 20mL Schlenk flask, 4.0mL of toluene and 1.0mL of tetrahydrofuran are added, the reaction mixture is stirred at 120 ℃ for 24 hours, cooled to room temperature, and 5mL of saturated NH is added 4 The results of GC analysis of the Cl aqueous solution (with mesitylene as the internal standard) are shown in Table seven.
Figure BDA0003048106460000134
Catalytic dehydrogenation coupling reaction of manganese complexes with different manganeseResults of preparation 3aa a
Figure BDA0003048106460000135
Figure BDA0003048106460000141
a Reaction conditions A:1.0mmol of 2-aminobenzyl alcohol, 2.0mmol of cycloheptanone, 2.0mmol of t-BuOK, 2.0mmol of KOH, 10.0 mmol of a compound represented by the formula 1 (Mn-1-Mn-5), 4.0mL of toluene, 1.0mL of THF,120 ℃ and 24 hours; reaction conditions B:1.0mmol of 2-aminobenzyl alcohol, 2.0mmol of cycloheptyl alcohol, 2.0mmol of t-BuOK, 2.0mmol of KOH, 50.0 mmol of the compound represented by the formula 1 (Mn-1-Mn-5), 4.0mL of toluene, 1.0mL of THF,120 ℃ and 48 hours; b the conversion and yield were determined by GC with mesitylene as internal standard. c 10.0 umol Mn-4,24h。
EXAMPLE 18 preparation of 2-substituted or 2, 3-substituted quinoline by dehydrogenation coupling reaction of O-aminobenzyl alcohol (1 a) with ketone (2) or secondary alcohol (2') catalyzed by Compound Mn-4 represented by formula 1
Reaction Condition A, using ketone as raw material, under nitrogen atmosphere, 121mg (1.0 mmol) of o-aminobenzyl alcohol, 2.0mmol (2 eq.) of ketone compound, 9.0mg (10umol, 1mol%) of Mn-4, 234mg (1.0 mmol) of t-BuOK, and 112mg (1.0 mmol) of KOH were put in a 20mL Schlenk bottle, and 4.0mL of toluene and 1.0mL of tetrahydrofuran were added, and the reaction mixture was stirred at 120 ℃ for reaction for 24 hours, cooled to room temperature, and 5mL of saturated NH was added 4 Aqueous Cl, ethyl acetate (3 × 10 mL), combined organic phases concentrated and spin dried, washed with ethyl acetate: petroleum ether =1 (volume ratio) TLC analysis and the crude product was purified by flash column chromatography using a gradient of petroleum ether and ethyl acetate (eluent system) (from pure petroleum ether to petroleum ether: ethyl acetate = 20) to give the pure quinoline product.
Reaction Condition B, using a secondary alcohol as a raw material, 121mg (1.0 mmol) of anthranilic alcohol, 2.0mmol (2 eq.) of a secondary alcohol compound, 9.0mg (10umol, 1mol%) of Mn-4, 234mg (1.0 mmol) of t-BuOK, and 112mg (1.0 mmol) of KOH were placed in a volume of 20mL of SchlenkIn a flask, 4.0mL of toluene and 1.0mL of tetrahydrofuran were added, the reaction mixture was stirred at 120 ℃ for 24 hours, cooled to room temperature, and 5mL of saturated NH was added 4 Aqueous Cl, ethyl acetate (3 × 10 mL), combined organic phases concentrated and spin dried, washed with ethyl acetate: petroleum ether = 1.
The results of the separation yield of the 2-substituted or 2, 3-substituted quinoline products are shown in the eight table
Figure BDA0003048106460000142
TABLE VIII preparation of 2-substituted or 2, 3-substituted quinolines by dehydrocoupling of O-aminobenzyl alcohol (1 a) with ketones (2) or secondary alcohols (2') catalyzed by Mn-4 a
Figure BDA0003048106460000151
a Reaction conditions A:1.0mmol of o-aminobenzyl alcohol, 2.0mmol of ketone, 2.0mmol of t-BuOK, 2.0mmol of KOH, 10.0 mmol of Mn-4, 4.0mL of toluene, 1.0mL of THF,120 ℃ and 24 hours; reaction conditions B:1.0mmol of o-aminobenzyl alcohol, 2.0mmol of secondary alcohol, 2.0mmol of t-BuOK, 2.0mmol of KOH, 50.0 mmol of Mn-4, 4.0mL of toluene, 1.0Ml of THF,120 ℃ and 48h; & represents the isolated yield of the quinoline product (3 b-3 v) under the reaction conditions A; Φ represents the isolated yield of the quinoline-like product (3B-3 v) under reaction conditions B.
EXAMPLE 19 preparation of polysubstituted quinoline derivatives by dehydrogenation coupling reaction of o-aminoarylols (1 b-1 e) and ketone (2) catalyzed by Compound Mn-4 shown in formula 1
Under a nitrogen atmosphere, 1.0mmol of an o-aminoaryl alcohol, 2.0mmol (2 eq.) of a ketone compound, 9.0mg (10umol, 1mol%) of Mn-4, 234mg (1.0 mmol) of t-BuOK, and 112mg (1.0 mmol) of KOH were placed in a 20mL Schlenk bottle, 4.0mL of toluene and 1.0mL of tetrahydrofuran were added, and the reaction mixture was stirredThe reaction was stirred at 120 ℃ for 24 hours, cooled to room temperature, and 5mL of saturated NH were added 4 Aqueous Cl, ethyl acetate (3 × 10 mL), combined organic phases concentrated and spin dried, washed with ethyl acetate: petroleum ether =1 (volume ratio) TLC analysis and purification of the crude product by flash column chromatography using a gradient of petroleum ether and ethyl acetate (eluent system) (from pure petroleum ether to petroleum ether: ethyl acetate = 20) gave the corresponding polysubstituted quinoline product.
The results of the separation yield of the polysubstituted quinoline products are shown in the table nine
Figure BDA0003048106460000152
TABLE 4 preparation of polysubstituted quinoline derivatives by dehydrogenation coupling reaction of o-aminoaryl alcohol and ketone (2) under catalysis of Mn-4 a
Figure BDA0003048106460000161
Reaction conditions are as follows: 1.0mmol of o-aminoaralkyl alcohol (1 b-1 e), 2.0mmol of ketone substrate, 2.0mmol of t-BuOK, 2.0mmol of KOH, 10. Mu. Mol of Mn-4,4mL of toluene, 1mL of THF,120 ℃ for 24 hours.
EXAMPLE 20 Synthesis of 2, 3-substituted or 2,3, 6-substituted pyridines by coupling cyclization of Gamma-aminoalcohol (1 f. About.1 h) with ketones catalyzed by Compound Mn-4 represented by formula 1
Under nitrogen protection, 1.0mmol of γ -amino alcohol, 2.0mmol (2 eq.) of ketones, 9.0mg (10umol, 1mol%) of Mn-4, 234mg (1.0 mmol) of t-BuOK, and 112mg (1.0 mmol) of KOH were placed in a 20mL Schlenk bottle, 4.0mL of toluene and 1.0mL of tetrahydrofuran were added, the reaction mixture was stirred at 120 ℃ for 24 hours, cooled to room temperature, and 5mL of saturated NH was added 4 Aqueous Cl, ethyl acetate (3 × 10 mL), combined organic phases concentrated and spin dried, washed with ethyl acetate: petroleum ether = 1.
The separation yield results of the polysubstituted pyridine products are shown in the table ten
Figure BDA0003048106460000162
TABLE 4 preparation of polysubstituted pyridine derivatives by dehydrogenation coupling reaction of gamma-amino alcohol (1 f-1 h) and ketone under catalysis of Mn-4 a
Figure BDA0003048106460000171
The reaction conditions were 1.0mmol of. Gamma. -amino alcohol (1 f-1 g), 2.0mmol of a ketone substrate, 2.0mmol of t-BuOK, 2.0mmol of KOH, 10. Mu. Mol of Mn-4,4mL of toluene, 1mL of THF,120 ℃ and 24 hours.
Br in the above-disclosed pincer-like manganese complexes - As anions, but the catalytic properties described above depend mainly on the cation complex, so that the anions are exchanged for other halogen ions such as Cl - 、I - 、F - Etc. or NO 3 - 、ClO 4 - The isovalent acid radical ions still have similar catalytic performance and are also within the conception and the protection scope of the invention.
The structures of the quinoline and pyridine derivatives are all characterized by NMR spectrum, and the structural data of part of the compounds are characterized as follows: 6,7,8,9,10,11,12,13,14,15-decahydrocyclododecyl [ b ] quinoline
Figure BDA0003048106460000172
Light yellow solid, mp 88-99 deg.C; 1 H NMR(400MHz,CDCl 3 )δ8.00(d,J＝8.5Hz,1H),7.88(s,1H),7.69(d,J＝8.1Hz,1H),7.60(t,J＝7.6Hz,1H),7.42(t,J＝7.4Hz,1H),3.02(t,J＝7.7Hz,2H),2.82(t,J＝7.8Hz,2H),1.94(d,J＝11.7Hz,2H),1.78(d,J＝13.4Hz,2H),1.58–1.41(m,12H). 13 C NMR(100MHz,CDCl 3 )δ161.62,145.54,134.72,133.79,127.35,126.11,125.76,124.48,31.67,28.71,28.62,27.45,25.68,25.44,24.99,24.41,22.06,21.97.
7,8,9,10,11,12,13,14,15,16,17, 18-dodecylhexahydro-cyclopenten [ b ] quinoline
Figure BDA0003048106460000173
Light yellow solid, mp is 101-103 deg.C; 1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.5Hz,1H),7.68(s,1H),7.56(d,J＝8.1Hz,1H),7.48(t,J＝7.6Hz,1H),7.30(t,J＝7.5Hz,1H),2.92–2.80(m,2H),2.70–2.57(m,2H),1.80–1.68(m,2H),1.63–1.55(m,2H),1.51–1.18(m,18H)； 13 C NMR(100MHz,CDCl 3 )δ161.86,146.15,134.84,133.90,128.02,126.93,126.44,125.15,35.47,34.89,32.01,28.93,27.89,27.03,26.79,26.50,26.45,26.27,26.24,25.64,25.20,22.90.
7-methyl-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecahexahydro-6H-cyclopent [ b ] quinoline
Figure BDA0003048106460000181
A light-yellow oily substance which is obtained by mixing, 1 H NMR(500MHz,CDCl 3 )δ8.03(d,J＝8.4Hz,1H),7.83(s,1H),7.69(d,J＝8.1Hz,1H),7.61–7.56(m,1H),7.45–7.38(m,1H),3.22(dd,J＝13.3,4.8Hz,1H),2.78(t,J＝8.2Hz,2H),2.67(dd,J＝13.3,10.0Hz,1H),2.19–2.06(m,1H),1.87–1.75(m,1H),1.72–1.65(m,1H),1.63–1.56(m,1H),1.49–1.31(m,17H),0.92(d,J＝6.6Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ160.24,145.10,133.71,133.52,127.55,127.21,126.23,125.75,124.50,42.63,35.12,30.53,30.35,27.40,26.35,25.49,25.39,25.37,24.95,24.89,24.61,24.00,18.33.
4-isopropyl-1-methyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000182
Light yellow oil, mp =101-102 ℃. 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.3Hz,1H),7.81(s,1H),7.64(t,J＝8.4Hz,1H),7.55–7.49(m,1H),7.38–7.32(m,1H),3.05–2.99(m,1H),2.91–2.84(m,1H),2.01–1.92(m,1H),1.84–1.78(m,1H),1.70-1.63(m,1H),1.31(dd,J＝18.5,7.0Hz,3H),1.19(d,J＝13.6Hz,2H),1.01(dd,J＝22.7,6.9Hz,3H),0.63(dd,J＝41.2,6.8Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ160.59,136.04,135.72,133.32,131.48,127.53,126.03,125.81,124.43,45.88,32.24,31.80,30.25,27.50,22.06,20.68,20.16,19.98.
2-phenyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000183
Light yellow solid, mp is 78-80 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.94(d,J＝8.5Hz,1H),7.75(s,1H),7.64(d,J＝8.1Hz,1H),7.55(t,J＝7.7Hz,1H),7.38(t,J＝7.5Hz,1H),7.31–7.22(m,4H),7.21–7.15(m,1H),3.31–3.23(m,1H),3.22–3.12(m,2H),3.04(d,J＝11.0Hz,2H),2.29–2.22(m,1H),2.15–2.01(m,1H),1.32–1.14(m,2H)； 13 C NMR(100MHz,CDCl 3 )δ158.71,147.00,145.93,135.44,130.61,129.06,128.91,128.57,127.40,127.25,127.10,126.79,126.03,40.67,37.64,33.86,30.71.
2-n-butyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000184
Pale yellow solid, mp is 59-60 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.98(d,J＝8.5Hz,1H),7.79(s,1H),7.69(d,J＝8.1Hz,1H),7.60(t,J＝7.6Hz,1H),7.42(t,J＝7.4Hz,1H),3.26–3.18(m,1H),3.12–3.02(m,2H),2.59(dd,J＝16.3,10.7Hz,1H),1.84–1.67(m,2H),1.60–1.53(m,1H),1.35–1.26(m,6H),0.90(d,J＝7.2Hz,3H)； 13 C NMR(125MHz,CDCl 3 )δ159.08,146.50,134.93,130.46,128.36,128.13,127.09,126.79,125.39,36.07,35.82,33.91,32.91,32.06,29.27,26.64,22.64,14.07.
2- (tert-butyl) -1,2,3, 4-tetrahydroacridine
Figure BDA0003048106460000191
Light yellow solid, mp 85-86 deg.C; 1 H NMR(500MHz,CDCl 3 )δ7.98(d,J＝8.5Hz,1H),7.79(s,1H),7.67(d,J＝8.1Hz,1H),7.61–7.56(m,1H),7.41(t,J＝7.5Hz,1H),3.31–3.23(m,1H),3.08–2.98(m,2H),2.70(dd,J＝16.0,11.5Hz,1H),2.20–2.12(m,1H),1.60–1.51(m,2H),0.99(s,9H)； 13 C NMR(125MHz,CDCl 3 )δ159.36,146.58,135.23,131.22,128.45,128.27,127.17,126.85,125.48,44.62,34.33,32.54,30.78,27.27,24.58.
11H-indeno [1,2-b ] quinolines
Figure BDA0003048106460000192
A light yellow oil; 1 H NMR(500MHz,CDCl 3 )δ8.22(d,J＝6.9Hz,1H),8.12(d,J＝8.4Hz,1H),8.07(s,1H),7.72(d,J＝8.1Hz,1H),7.60(dd,J＝12.6,5.5Hz,2H),7.51(d,J＝6.7Hz,1H),7.43–7.39(m,2H),3.93(s,2H). 13 C NMR(100MHz,CDCl 3 )δ160.63,146.98,144.04,139.29,133.55,130.12,128.93,128.04,127.78,126.73,126.48,124.63,124.41,121.04,32.96.
5, 6-dihydrobenzo [ c ] acridine
Figure BDA0003048106460000193
White solid, mp 62-63 deg.C; 1 H NMR(500MHz,CDCl 3 )δ8.12(d,J＝8.4Hz,1H),7.80(s,1H),7.75(d,J＝7.2Hz,1H),7.66(d,J＝8.0Hz,1H),7.56(t,J＝7.5Hz,1H),7.38(t,J＝7.4Hz,1H),7.12(d,J＝7.1Hz,1H),7.03–6.98(m,1H),6.93(d,J＝7.0Hz,1H),2.53(d,J＝6.8Hz,2H),2.43(t,J＝7.0Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ159.19,146.10,138.91,138.08,133.60,132.11,128.16,127.92,127.71,127.27,126.61,125.91,125.82,125.55,125.14,124.85,29.72,29.36.
6, 7-dihydro-5H-benzo [6,7] cyclohepta [1,2-b ] quinoline
Figure BDA0003048106460000194
White solid, mp 66-67 deg.C; 1 H NMR(400MHz,CDCl 3 )δ8.46(d,J＝7.2Hz,1H),8.00(d,J＝8.2Hz,1H),7.65(s,1H),7.49(dd,J＝20.3,7.9Hz,2H),7.27(t,J＝7.4Hz,2H),7.19(d,J＝7.1Hz,1H),7.08(d,J＝7.3Hz,1H),2.83(dd,J＝31.5,6.1Hz,4H),1.14(d,J＝9.2Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ153.18,147.46,139.24,134.55,133.52,130.38,129.52,129.25,128.47,127.80,127.70,127.15,126.80,125.93,125.87,29.62,28.61,28.20.
5, 6-dihydrobenzo [ b ] [1,10] phenanthroline
Figure BDA0003048106460000201
Purple solid, mp 89-90 deg.C; 1 H NMR(500MHz,CDCl 3 )δ8.77(s,1H),8.35(d,J＝6.9Hz,1H),7.93(d,J＝6.3Hz,1H),7.72(d,J＝6.5Hz,1H),7.66-7.62(m,1H),7.58-7.54(m,1H),7.51–7.44(m,1H),7.24(d,J＝4.3Hz,1H),3.12(d,J＝5.5Hz,2H),3.00(d,J＝5.6Hz,2H). 13 C NMR(100MHz,CDCl 3 )δ156.76,151.18,150.58,148.21,146.80,135.13,133.21,130.40,129.35,127.84,125.82,125.76,122.92,121.39,27.01,26.64.
6, 7-dihydro-5H-pyridine [3',2':6,7] cyclohepta [1,2-b ] quinoline
Figure BDA0003048106460000202
Light yellow solid, mp:132-134 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.72(dd,J＝4.8,1.3Hz,1H),8.28(d,J＝8.5Hz,1H),7.91(s,1H),7.73(d,J＝8.1Hz,1H),7.64–7.59(m,1H),7.50(d,J＝1.1Hz,1H),7.45(dd,J＝11.1,3.8Hz,1H),7.22(dd,J＝7.6,4.8Hz,1H),2.61(t,J＝7.0Hz,2H),2.47(t,J＝7.0Hz,2H),2.17–2.11(m,2H)； 13 C NMR(125MHz,CDCl 3 )δ158.31,156.82,148.62,147.49,136.61,135.12,135.10,132.69,130.12,128.89,126.86,123.64,118.21,117.84,31.20,29.87,29.55.
5,6,7, 8-tetrahydropyrido [3',2':7,8] cyclooctyl [1,2-b ] quinoline
Figure BDA0003048106460000203
Light yellow solid, mp:163-164 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.62(d,J＝4.0Hz,1H),8.20(d,J＝8.5Hz,1H),8.01(s,1H),7.77(d,J＝8.1Hz,1H),7.64(t,J＝7.6Hz,1H),7.57(d,J＝7.6Hz,1H),7.49(t,J＝7.5Hz,1H),7.30(dd,J＝7.6,4.8Hz,1H),2.89(dd,J＝13.8,7.9Hz,1H),2.70(dd,J＝13.8,8.0Hz,1H),2.35–2.28(m,1H),2.19(dd,J＝17.0,8.2Hz,2H),2.13–2.04(m,1H),1.67–1.51(m,3H). 13 C NMR(125MHz,CDCl 3 )δ157.69,155.98,147.40,146.58,137.40,136.02,129.49,128.77,128.21,126.65,126.52,123.73,117.65,115.59,31.34,31.24,30.52,29.04.
3, 4-dihydro-2H-1, 4-ethylbenzo [ b ] [1,5] naphthyridine
Figure BDA0003048106460000204
White solid, mp 121-123 deg.C; 1 H NMR(400MHz,CDCl 3 )δ8.06(d,J＝8.4Hz,1H),7.79(d,J＝7.4Hz,2H),7.65(t,J＝7.6Hz,1H),7.47(t,J＝7.5Hz,1H),3.41(s,1H),3.31–3.23(m,2H),2.79(td,J＝12.0,4.7Hz,2H),2.06(d,J＝10.9Hz,2H),1.79(d,J＝10.4Hz,2H)； 13 C NMR(100MHz,CDCl 3 )δ165.85,146.54,143.43,128.74,128.62,128.57,128.02,127.72,125.69,49.57,34.18,27.56.
2- (5-methylfuran-2-yl) quinoline
Figure BDA0003048106460000211
White solid, mp 120-121 deg.C; 1 H NMR(400MHz,CDCl 3 )δ8.11(d,J＝8.5Hz,2H),7.75(t,J＝7.7Hz,2H),7.68(t,J＝7.6Hz,1H),7.46(t,J＝7.4Hz,1H),7.12(s,1H),6.18(s,1H),2.46(s,3H)； 13 C NMR(100MHz,CDCl 3 ) Delta 153.51,151.04,148.10,147.03,135.44,128.66,128.16,126.46,125.87,124.80,116.24,110.50,107.60,12.99.2- (thien-2-yl) quinoline
Figure BDA0003048106460000212
Brown solid, mp 130-131 ℃; 1 H NMR(400MHz,CDCl 3 )δ8.11(t,J＝7.8Hz,2H),7.74(dt,J＝19.9,8.2Hz,4H),7.53–7.44(m,2H),7.16(s,1H)； 13 C NMR(100MHz,CDCl 3 )δ151.25,147.03,144.32,135.53,128.73,128.18,127.51,127.01,126.41,126.10,125.02,124.78,116.56.
2- (pyridin-2-yl) quinolines
Figure BDA0003048106460000213
White solid, mp 93-94 deg.C; 1 H NMR(400MHz,CDCl 3 )δ8.74(d,J＝3.7Hz,1H),8.66(d,J＝7.9Hz,1H),8.56(d,J＝8.5Hz,1H),8.27(d,J＝8.6Hz,1H),8.18(d,J＝8.4Hz,1H),7.85(t,J＝9.4Hz,2H),7.73(t,J＝7.6Hz,1H),7.54(t,J＝7.4Hz,1H),7.38–7.31(m,1H)； 13 C NMR(100MHz,CDCl 3 )δ155.24,155.07,148.08,146.84,135.86,135.72,128.74,128.48,127.16,126.55,125.67,122.95,120.75,117.87.
11-phenyl-7,8,9,10-tetrahydro-6H-cyclohepta [ b ] quinoline
Figure BDA0003048106460000214
Pale yellow solid, mp:126-127 ℃. 1 H NMR(500MHz,CDCl 3 )δ8.06(d,J＝8.4Hz,1H),7.61(ddd,J＝8.3,6.5,1.7Hz,1H),7.55–7.46(m,3H),7.32(dtd,J＝9.8,8.4,1.3Hz,2H),7.27–7.24(m,2H),3.32(d,J＝4.8Hz,2H),2.75–2.70(m,2H),1.88(d,J＝2.6Hz,4H),1.63(d,J＝4.2Hz,2H)； 13 C(125MHz,CDCl 3 )δ164.76,145.86,145.48,137.67,133.81,129.46,128.62,128.44,128.19,127.64,126.95,126.35,125.58,40.17,31.93,30.70,28.53,27.07.
2-chloro-7,8,9,10-tetrahydro-6H-cyclohepta [ b ] quinoline
Figure BDA0003048106460000221
Light yellow solid, mp is 121-122 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.89(d,J＝8.9Hz,1H),7.64(s,1H),7.62(s,1H),7.51(dd,J＝8.9,1.2Hz,1H),3.18–3.13(m,2H),2.91–2.85(m,2H),1.86(d,J＝5.1Hz,2H),1.79–1.66(m,4H). 13 C NMR(125MHz,CDCl 3 )δ165.01,144.57,137.54,133.54,131.29,130.07,129.24,127.98,125.48,77.35,77.10,76.84,39.99,35.39,32.15,28.72,26.90.
2-methyl-7,8,9,10-tetrahydro-6H-cyclohepta [ b ] quinoline
Figure BDA0003048106460000222
Light yellow solid, mp is 99-100 deg.C; 1 H NMR(500MHz,CDCl 3 )δ7.90(d,J＝8.3Hz,1H),7.72(s,1H),7.47(s,1H),7.46–7.43(m,1H),3.23–3.17(m,2H),2.93(dd,J＝6.6,4.5Hz,2H),2.50(s,3H),1.89(dd,J＝11.0,5.6Hz,2H),1.82–1.71(m,4H)； 13 C NMR(100MHz,CDCl 3 )δ163.68,144.76,136.45,135.44,134.06,130.68,128.11,127.38,125.76,39.97,35.49,32.27,28.90,27.07,21.53.
7-chloro-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000223
Light yellow solid, mp 85-86 deg.C; 1 H NMR(400MHz,CDCl 3 )δ7.82(d,J＝8.9Hz,1H),7.62(s,1H),7.58(s,1H),7.45(d,J＝8.9Hz,1H),3.03(t,J＝6.2Hz,2H),2.89(t,J＝5.8Hz,2H),1.91(d,J＝5.8Hz,2H),1.82(d,J＝5.2Hz,2H)； 13 C NMR(125MHz,CDCl 3 )δ159.74,144.93,133.98,132.05,131.09,129.92,129.36,127.76,125.49,33.50,29.25,23.09,22.76.
7-methyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000224
Light yellow solid, mp:52-53 deg.C; 1 H NMR(400MHz,CDCl 3 )δ7.86(d,J＝9.0Hz,1H),7.68(s,1H),7.42(d,J＝7.1Hz,2H),3.10(t,J＝6.4Hz,2H),2.93(t,J＝6.0Hz,2H),2.48(s,3H),2.00–1.93(m,2H),1.87(dd,J＝10.3,5.0Hz,2H)； 13 C NMR(125MHz,CDCl 3 )δ158.19,145.11,135.16,134.42,130.81,127.85,127.23,125.70,33.36,29.24,23.25,22.93,21.50.
2-chloro-6,7,8,9,10,11-hexahydrocyclooctatetra [ b ] quinoline
Figure BDA0003048106460000225
Light yellow solid, mp is 110-111 ℃; 1 H NMR(400MHz,CDCl 3 )δ7.94(d,J＝8.9Hz,1H),7.72(s,1H),7.67(s,1H),7.53(d,J＝8.9Hz,1H),3.17–3.09(m,2H),2.96–2.88(m,2H),1.89-1.86(m,2H),1.79-1.74(m,2H),1.42-1.38(m,4H)； 13 C NMR(125MHz,CDCl 3 )δ163.62,145.29,136.22,134.02,131.15,130.13,129.25,128.20,125.51,35.24,32.64,32.04,30.91,26.02,25.87.
2-methyl-6,7,8,9,10,11-hexahydrocycloocta [ b ] quinoline
Figure BDA0003048106460000231
Light yellow solid, mp:84-85 deg.C; 1 H NMR(400MHz,CDCl 3 )δ7.92(d,J＝8.5Hz,1H),7.74(s,1H),7.49–7.42(m,2H),3.17–3.11(m,2H),2.95–2.89(m,2H),2.50(s,3H),1.90-1.80(m,2H),1.78-1.71(m,2H),1.42-1.38(m,4H)； 13 C NMR(100MHz,CDCl 3 )δ162.16,145.49,135.25,135.07,134.46,130.69,128.15,127.64,125.73,35.17,32.74,32.06,31.01,26.07,25.91,21.53.
16-methyl-6,7,8,9,10,11,12,13,14,15-decahydrocyclodododec [ b ] quinoline
Figure BDA0003048106460000232
Light yellow solid, mp is 102-103 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.97(d,J＝8.4Hz,1H),7.73–7.68(m,2H),7.63(ddd,J＝8.2,6.9,1.2Hz,1H),7.51–7.46(m,1H),3.11–3.03(m,4H),2.98–2.92(m,2H),2.68(s,3H),2.00–1.92(m,2H),1.73(ddd,J＝14.3,10.0,7.1Hz,2H),1.63(t,J＝7.6Hz,6H),1.56–1.48(m,6H)； 13 C NMR(125MHz,CDCl 3 )δ162.28,146.74,144.62,132.36,130.13,129.76,129.38,129.24,129.09,128.06,127.09,125.87,125.40,123.56,123.50,121.05,117.25,34.38,28.55,27.97,27.90,27.44,27.35,26.77,22.99,22.66,14.53.
16-phenyl-6, 7,8,9,10,11,12,13,14, 15-decahydrocyclododecyl [ b ] quinoline
Figure BDA0003048106460000233
Light yellow solid, 131-132 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.07(d,J＝8.4Hz,1H),7.61(ddd,J＝8.3,6.8,1.4Hz,1H),7.54–7.48(m,3H),7.34–7.29(m,1H),7.29–7.26(m,2H),7.22(dd,J＝8.4,0.9Hz,1H),3.14–3.09(m,2H),2.70–2.65(m,2H),2.11–2.04(m,2H),1.67(dd,J＝11.0,6.7Hz,2H),1.64–1.59(m,2H),1.54–1.48(m,6H),1.36–1.27(m,4H)； 13 C NMR(125MHz,CDCl 3 )δ162.65,147.30,146.08,137.81,132.16,129.42,128.41,128.28,127.63,126.91,126.14,125.43,33.87,28.91,28.58,28.38,28.08,27.82,27.14,26.95,23.30,22.87.
2-chloro-6,7,8,9,10,11,12,13,14,15-decahydrocyclododecyl [ b ] quinoline
Figure BDA0003048106460000234
Light yellow solid, 113-114 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.9Hz,1H),7.80(s,1H),7.68(d,J＝2.2Hz,1H),7.53(dd,J＝9.0,2.3Hz,1H),3.04–2.99(m,2H),2.85–2.79(m,2H),1.99–1.92(m,2H),1.79(ddd,J＝14.0,10.0,6.9Hz,2H),1.54(dd,J＝14.2,6.2Hz,4H),1.49(dd,J＝11.9,6.4Hz,4H),1.42(d,J＝3.1Hz,4H)； 13 C NMR(125MHz,CDCl 3 )δ163.10,144.88,135.95,134.85,131.15,130.02,129.31,127.75,125.45,32.67,29.69,28.38,26.70,26.45,25.99,25.44,23.16,23.09.
2-methyl-6,7,8,9,10,11,12,13,14,15-decahydrocyclododecyl [ b ] quinoline
Figure BDA0003048106460000241
Light yellow solid, mp is 99-100 deg.C; 1 H NMR(500MHz,CDCl 3 )δ7.92(d,J＝8.0Hz,1H),7.82(s,1H),7.47(s,1H),7.45(d,J＝8.6Hz,1H),3.02(t,J＝7.8Hz,2H),2.85–2.79(m,2H),2.50(s,3H),2.00–1.93(m,2H),1.83–1.76(m,2H),1.55(dd,J＝13.1,6.2Hz,4H),1.49(dd,J＝12.1,6.4Hz,4H),1.42(d,J＝3.0Hz,4H)； 13 C NMR(100MHz,CDCl 3 )δ160.58,144.04,134.22,133.74,129.71,126.95,126.14,124.61,31.54,28.71,28.64,27.48,25.70,25.47,25.03,24.43,22.09,22.01,20.48.
19-methyl-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecyl-6H-cyclopent [ b ] quinoline
Figure BDA0003048106460000242
Pale yellow solid, 108-110 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.01(d,J＝8.3Hz,1H),7.94(d,J＝8.4Hz,1H),7.59(t,J＝7.5Hz,1H),7.45(t,J＝7.6Hz,1H),3.02–2.96(m,2H),2.83–2.77(m,2H),2.62(s,3H),1.88–1.81(m,2H),1.57–1.53(m,2H),1.49–1.45(m,4H),1.38–1.33(m,14H)； 13 C NMR(125MHz,CDCl 3 )δ160.64,144.88,139.73,131.09,128.08,126.81,126.05,124.24,122.32,116.21,35.51,28.33,27.38,27.12,26.75,26.64,26.10,25.40,25.25,24.95,24.37,24.27,22.19,13.03.
19-phenyl-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecyl-6H-cyclopent [ b ] quinoline
Figure BDA0003048106460000243
Light yellow solid, 121-122 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.12(d,J＝8.3Hz,1H),7.67–7.62(m,1H),7.58–7.50(m,3H),7.35(dd,J＝11.2,3.9Hz,1H),7.32–7.26(m,3H),3.14–3.07(m,2H),2.62–2.56(m,2H),2.04–1.95(m,2H),1.71(d,J＝6.6Hz,2H),1.55-1.51(m,4H),1.43–1.33(m,14H)； 13 C NMR(125MHz,CDCl 3 )δ162.30,137.70,132.13,129.28,128.34,127.67,127.01,126.20,125.48,35.99,30.00,29.71,29.19,28.19,27.81,27.70,26.85,26.60,26.31,26.09,25.49,25.39,23.47.
2-chloro-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecyl-6H-cyclopentatetra [ b ] quinoline
Figure BDA0003048106460000244
Pale yellow solid, 117-118 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.96(d,J＝8.9Hz,1H),7.78(s,1H),7.69(s,1H),7.55(dd,J＝8.9,2.1Hz,1H),3.01–2.95(m,2H),2.83–2.77(m,2H),1.87–1.79(m,2H),1.77–1.70(m,2H),1.62–1.55(m,4H),1.49–1.44(m,4H),1.39-1.34(m,10H)； 13 C NMR(125MHz,CDCl 3 )δ162.76,144.83,135.49,134.28,131.15,130.04,129.24,127.89,125.49,77.30,77.04,76.79,35.78,32.40,29.24,28.10,27.54,27.41,26.86,26.82,26.80,26.61,26.05,25.92,25.68,25.63,23.13.
2-methyl-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecyl-6H-cyclopent [ b ] quinoline
Figure BDA0003048106460000251
Pale yellow solid, mp 116-117 deg.C 1 H NMR(500MHz,CDCl 3 )δ7.91(d,J＝8.4Hz,1H),7.76(s,1H),7.46(s,1H),7.44(d,J＝8.6Hz,1H),2.96(dd,J＝10.0,6.8Hz,2H),2.80–2.74(m,2H),2.50(s,3H),1.85–1.78(m,2H),1.75–1.69(m,2H),1.60–1.53(m,4H),1.47–1.42(m,4H),1.35(d,J＝3.3Hz,10H)； 13 C NMR(125MHz,CDCl 3 )δ161.28,145.18,135.10,134.59,134.23,130.55,128.16,127.31,125.70,35.83,32.46,29.36,28.26,27.58,27.45,26.90,26.87,26.63,26.06,25.92,25.65,25.60,21.49.
2-chloro-7-methyl-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecyl-6H-cyclopenteno [ b ] quinoline
Figure BDA0003048106460000252
Light yellow solid, mp is 125-126 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.9Hz,1H),7.69(s,1H),7.63(s,1H),7.49(dd,J＝8.9,2.3Hz,1H),3.17(dd,J＝13.4,4.7Hz,1H),2.73(t,J＝8.1Hz,2H),2.62(dd,J＝13.4,10.0Hz,1H),2.08(dd,J＝9.0,5.2Hz,1H),1.80–1.71(m,1H),1.68–1.60(m,1H),1.58–1.52(m,1H),1.48(dd,J＝12.8,6.5Hz,1H),1.44–1.25(m,16H),0.90(d,J＝6.6Hz,3H). 13 C NMR(125MHz,CDCl 3 )δ160.60,143.47,134.53,132.59,130.04,129.26,127.99,126.80,124.39,42.49,35.10,30.51,30.30,27.28,26.29,25.47,25.41,25.37,24.90,24.65,23.97,18.39.
2, 7-dimethyl-7, 8,9,10,11,12,13,14,15,16,17, 18-dodecyl-6H-cyclopenten [ b ] quinoline
Figure BDA0003048106460000253
Light yellow solid, 123-124 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.3Hz,1H),7.77(s,1H),7.47(s,1H),7.44(d,J＝8.6Hz,1H),3.21(dd,J＝13.3,4.9Hz,1H),2.78(t,J＝8.2Hz,2H),2.70–2.61(m,1H),2.50(s,3H),2.11(dt,J＝10.9,6.3Hz,1H),1.86–1.78(m,1H),1.73–1.66(m,1H),1.59(dd,J＝13.3,6.6Hz,1H),1.55–1.51(m,1H),1.47–1.31(m,16H),0.91(d,J＝6.6Hz,3H)； 13 C NMR(100MHz,CDCl 3 )δ159.28,143.64,134.23,133.51,133.23,129.52,127.23,126.27,124.67,42.57,35.12,30.59,30.40,27.48,26.39,25.56,25.43,25.41,24.99,24.94,24.66,24.04,20.49,18.34.
7-chloro-2-phenyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000261
Light yellow solid, 94-96 deg.C; 1 H NMR(500MHz,CDCl 3 )δ7.95(d,J＝9.0Hz,1H),7.75(s,1H),7.71(s,1H),7.57(dd,J＝9.0,2.2Hz,1H),7.37(t,J＝7.5Hz,2H),7.33–7.31(m,2H),7.28(dd,J＝9.4,2.2Hz,1H),3.33-3.31(m,1H),3.29–3.22(m,2H),3.13(d,J＝10.7Hz,2H),2.38–2.32(m,1H),2.21–2.13(m,1H)； 13 C NMR(125MHz,CDCl 3 )δ157.76,144.34,144.02,132.93,130.27,130.14,128.93,128.46,127.58,126.56,125.69,125.49,124.47,39.15,36.20,32.48,29.23.
7-methyl-2-phenyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000262
Pale yellow solid, 85-87 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.93(d,J＝8.2Hz,1H),7.77(d,J＝3.5Hz,1H),7.49(s,1H),7.33–7.27(m,4H),7.22–7.19(m,2H),3.70(td,J＝10.8,5.4Hz,1H),3.30–3.20(m,2H),3.17–3.09(m,2H),2.52(s,3H),1.97–1.89(m,2H)； 13 C NMR(125MHz,CDCl 3 )δ157.42,145.79,145.39,135.45,134.61,131.16,130.30,128.67,128.41,128.00,126.88,126.84,126.53,37.40,36.06,33.47,30.52,
2- (tert-butyl) -9-phenyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000263
Light yellow solid, mp is 102-103 deg.C; 1 H NMR(500MHz,CDCl 3 )δ8.06(d,J＝5.5Hz,1H),7.61(dd,J＝11.8,3.8Hz,1H),7.53(dd,J＝10.6,5.1Hz,2H),7.47(t,J＝7.4Hz,1H),7.33(d,J＝3.3Hz,2H),7.25–7.21(m,2H),3.36(d,J＝16.9Hz,1H),3.14(ddd,J＝17.4,11.4,5.6Hz,1H),2.73–2.64(m,1H),2.32(dd,J＝16.7,11.6Hz,1H),2.18–2.11(m,1H),1.58–1.47(m,2H),0.85(s,9H)； 13 C NMR(125MHz,CDCl 3 )δ159.27,146.83,146.13,137.01,129.17,128.93,128.85,128.75,128.66,128.60,128.40,128.24,127.78,126.69,125.83,125.40,44.73,34.79,32.59,29.33,27.15,24.16.
2- (tert-butyl) -7-chloro-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000264
Light yellow solid, mp 86-87 deg.C; 1 H NMR(500MHz,CDCl 3 )δ7.91(d,J＝6.7Hz,1H),7.74(s,1H),7.67(s,1H),7.53(dd,J＝9.0,2.2Hz,1H),3.07–2.98(m,2H),2.72(dd,J＝15.9,11.4Hz,1H),2.21–2.14(m,1H),1.78(d,J＝11.7Hz,1H),1.60–1.54(m,2H),1.00(s,9H). 13 C NMR(125MHz,CDCl 3 )δ158.82,143.86,133.26,131.37,130.05,128.86,128.33,126.72,124.44,43.49,35.09,33.22,31.53,29.78,26.22,24.59,23.44.
2- (tert-butyl) -7-methyl-1, 2,3, 4-tetrahydroacridine
Figure BDA0003048106460000271
Light yellow solid, mp is 81-82 ℃; 1 H NMR(500MHz,CDCl 3 )δ7.76(d,J＝8.4Hz,1H),7.51(s,1H),7.26(d,J＝10.0Hz,2H),2.86(ddd,J＝31.0,18.4,11.0Hz,2H),2.50(dd,J＝15.7,11.7Hz,1H),2.33(s,3H),1.88(d,J＝10.5Hz,1H),1.61(d,J＝11.0Hz,1H),1.41–1.32(m,2H),1.12(d,J＝13.6Hz,1H),0.85(s,9H)； 13 C NMR(125MHz,CDCl 3 )δ157.11,143.99,133.97,133.62,129.98,129.69,126.75,126.12,124.58,35.02,32.96,31.41,29.66,26.59,26.19,24.61,23.49,20.42.
6-chloro-2- (pyridin-2-yl) quinolines
Figure BDA0003048106460000272
Light yellow solid, mp is 121-122 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.73(d,J＝4.7Hz,1H),8.64(d,J＝7.9Hz,1H),8.52(d,J＝8.6Hz,1H),8.19(dd,J＝8.6,2.6Hz,1H),8.08(d,J＝8.6Hz,1H),7.89–7.84(m,1H),7.61(s,1H),7.57(d,J＝8.6Hz,1H),7.37–7.32(m,1H)； 13 C NMR(125MHz,CDCl 3 )δ155.25,155.06,148.11,148.07,135.82,135.80,135.66,134.68,130.31,129.34,128.76,128.44,126.52,125.64,125.20,123.09,122.91,120.73,120.67,118.71,117.87.
6-methyl-2- (pyridin-2-yl) quinolines
Figure BDA0003048106460000273
Light yellow solid, mp 115-116 deg.C; 1 H NMR(500MHz,CDCl 3 )δ8.72(d,J＝4.2Hz,1H),8.63(d,J＝8.0Hz,1H),8.51(d,J＝8.6Hz,1H),8.15(d,J＝8.6Hz,1H),8.07(d,J＝8.5Hz,1H),7.82(td,J＝7.7,1.7Hz,1H),7.57–7.51(m,2H),7.30(ddd,J＝7.4,4.8,0.9Hz,1H),2.51(s,3H)； 13 C NMR(125MHz,CDCl 3 )δ156.50,155.34,149.13,146.53,136.87,136.69,136.09,131.85,129.51,128.29,126.51,123.84,121.69,118.95,21.64.
5,6,7,8,9,10,11,12,13,14-decahydrocyclododecyl [ b ] pyridine
Figure BDA0003048106460000274
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ8.40(dd,J＝4.7,1.6Hz,1H),7.46(dd,J＝7.7,1.4Hz,1H),7.05(dd,J＝7.7,4.7Hz,1H),2.85(t,J＝7.5Hz,2H),2.69–2.65(m,2H),1.88(dd,J＝6.5,5.1Hz,2H),1.74–1.69(m,4H),1.53–1.50(m,4H),1.41(dd,J＝5.9,3.2Hz,6H)； 13 C NMR(125MHz,CDCl 3 )δ159.39,145.55,136.36,135.12,120.00,41.56,39.35,34.04,30.41,28.68.
6,7,8,9,10,11,12,13,14,15,16,17-dodecylhydrido 5H-cyclopentylpyridin
Figure BDA0003048106460000281
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ8.35(dd,J＝4.8,1.6Hz,1H),7.40(dd,J＝7.6,1.5Hz,1H),7.02(dd,J＝7.6,4.8Hz,1H),3.71(dd,J＝12.0,6.0Hz,2H),2.80–2.75(m,2H),2.61–2.56(m,2H),1.74–1.70(m,2H),1.56(d,J＝7.4Hz,4H),1.48(dd,J＝6.4,3.0Hz,4H),1.42–1.36(m,10H)； 13 C NMR(100MHz,CDCl 3 )δ160.45,146.65,137.12,135.69,121.10,35.01,32.45,29.55,28.31,27.50,27.12,25.98,25.49.
2-methyl-5,6,7,8,9,10,11,12,13,14-decahydrocyclododecyl [ b ] pyridine
Figure BDA0003048106460000282
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ7.32(d,J＝7.8Hz,1H),6.88(d,J＝7.7Hz,1H),2.79(t,J＝7.5Hz,2H),2.60(t,J＝7.6Hz,2H),2.48(s,3H),1.89–1.80(m,2H),1.70–1.64(m,2H),1.50(d,J＝5.4Hz,4H),1.42-1.32(m,8H)； 13 C NMR(100MHz,CDCl 3 )δ158.59,153.93,136.53,131.61,119.57,30.61,28.36,27.60,27.38,25.12,24.96,24.63,24.05,23.08,21.91,21.73.
2-methyl-6,7,8,9,10,11,12,13,14,15,16,17-dodecylhydro-5H-cyclopentyl
Figure BDA0003048106460000283
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ7.30(d,J＝7.6Hz,1H),6.89(d,J＝7.7Hz,1H),2.80–2.71(m,2H),2.59–2.53(m,2H),2.49(s,3H),1.72–1.66(m,2H),1.59(dd,J＝9.7,6.1Hz,2H),1.54–1.47(m,4H),1.44–1.38(m,6H),1.36–1.31(m,8H)； 13 C NMR(125MHz,CDCl 3 )δ159.64,154.88,137.63,132.38,125.50,35.25,32.06,29.69,28.67,27.51,27.46,26.94,26.91,26.69,26.11,25.97,25.46,25.45.
2-phenyl-5, 6,7,8,9,10,11,12,13, 14-decahydrocyclododecyl [ b ] pyridine
Figure BDA0003048106460000284
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ8.01–7.97(m,2H),7.46(dt,J＝15.1,9.1Hz,4H),7.37(d,J＝7.3Hz,1H),2.70(t,J＝7.5Hz,2H),2.00–1.95(m,2H),1.76–1.71(m,2H),1.52(dd,J＝10.2,6.3Hz,4H),1.40(dd,J＝9.7,6.9Hz,8H),1.32–1.26(m,2H)； 13 C NMR(125MHz,CH 2 Cl 2 )δ159.25,153.17,138.85,136.81,133.29,127.52,127.28,125.71,116.62,30.51,28.42,27.65,26.90,25.03,24.62,24.14,24.09,22.03,21.99.
2-phenyl-6, 7,8,9,10,11,12,13,14,15,16, 17-dodecylhydro-5H-cyclopent [ b ] pyridine
Figure BDA0003048106460000285
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ7.92–7.86(m,2H),7.36–7.28(m,4H),7.24(t,J＝7.3Hz,1H),2.79–2.72(m,2H),2.54–2.47(m,2H),1.77–1.70(m,2H),1.56–1.51(m,2H),1.48–1.44(m,2H),1.40(dd,J＝9.1,4.3Hz,2H),1.32(d,J＝6.7Hz,4H),1.24(d,J＝2.6Hz,10H)； 13 C NMR(100MHz,CDCl 3 )δ159.06,153.16,138.86,136.60,132.97,127.50,127.21,125.69,116.66,33.96,31.12,28.51,27.07,26.49,26.41,25.97,25.87,25.67,25.02,24.97,24.61.
8-isopropyl-5-methyl-5, 6,7, 8-tetrahydroquinoline
Figure BDA0003048106460000291
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ8.41(dd,J＝4.4,2.1Hz,1H),7.53(d,J＝7.8Hz,1H),7.07–7.02(m,1H),2.78(ddd,J＝9.5,7.6,3.3Hz,2H),1.99–1.90(m,2H),1.81(tdd,J＝16.9,5.8,3.4Hz,2H),1.27(d,J＝6.5Hz,3H),1.07–1.03(m,3H),0.69–0.61(m,3H)； 13 C NMR(125MHz,CDCl 3 )δ158.52(J＝31.3Hz),145.31(J＝32.7Hz),135.33,127.57(J＝4.2Hz),119.65(J＝9.2Hz),45.11(J＝36.5Hz),31.63(J＝25.4Hz),29.83(J＝19.8Hz),28.68,20.21(J＝14.2Hz),19.84(J＝14.2Hz).
6-phenyl-5, 6,7, 8-tetrahydroquinoline
Figure BDA0003048106460000292
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ8.38(d,J＝4.4Hz,1H),7.35-7.19(m,6H),7.03(dd,J＝7.5,4.9Hz,1H),3.11–3.05(m,1H),2.50–2.44(m,2H),2.22–2.16(m,2H),2.05–1.85(m,2H)； 13 C NMR(100MHz,CDCl 3 )δ155.60,145.99,144.69,135.69,130.66,127.55,127.53,125.73,125.62,125.52,125.38,119.98,39.09,35.83,31.61,29.12.
2, 6-diphenyl-5, 6,7, 8-tetrahydroquinoline
Figure BDA0003048106460000293
Light yellow solid, mp =128-129 ℃. 1 H NMR(500MHz,CDCl 3 )δ8.01(d,J＝7.6Hz,2H),7.48(dt,J＝17.0,8.7Hz,4H),7.42(d,J＝6.6Hz,1H),7.37(d,J＝7.0Hz,2H),7.32(d,J＝7.4Hz,2H),7.28(d,J＝6.5Hz,1H),3.25–3.13(m,2H),3.11–3.04(m,2H),3.03–2.97(m,1H),2.31–2.27(m,1H),2.15-2.07(m,1H)； 13 C NMR(100MHz,CDCl 3 )δ156.62,155.03,145.96,139.82,137.45,130.18,128.75,128.65,128.58,126.93,126.90,126.48,118.07,40.37,36.80,33.13,30.41.
2-phenyl-5, 6-dihydrobenzo [ h ] quinolines
Figure BDA0003048106460000294
Light yellow solid, mp.92-95 ℃, 1 H NMR(500MHz,CDCl 3 )δ7.78(dd,J＝6.7,2.6Hz,1H),7.72–7.67(m,1H),7.47(d,J＝7.4Hz,2H),7.40(dt,J＝12.9,4.5Hz,4H),7.35–7.30(m,1H),7.22(t,J＝5.8Hz,1H),7.18(d,J＝8.3Hz,1H),3.09(ddd,J＝16.1,10.2,5.6Hz,1H),2.90–2.83(m,1H),2.26–2.19(m,1H),2.17–2.07(m,1H)； 13 C NMR(125MHz,CDCl 3 )δ155.15,152.16,139.79,138.32,135.00,130.40,128.74,128.43,127.65,125.16,124.91,118.85,30.81,26.93.
6-methyl-2, 2' -bipyridine
Figure BDA0003048106460000301
A light yellow oil, and a white pigment, 1 H NMR(500MHz,CDCl 3 )δ8.66(br,1H),8.41–8.35(m,1H),8.16(d,J＝7.8Hz,1H),7.80(d,J＝7.5Hz,1H),7.69(t,J＝7.7Hz,1H),7.28(dd,J＝7.4,4.1Hz,1H),7.16(d,J＝7.6Hz,1H),2.63(s,3H)； 13 C NMR(100MHz,CDCl 3 )δ156.84(J＝16.3Hz),155.56(J＝14.3Hz),154.47(J＝17.6Hz),148.07(J＝9.2Hz),135.93(J＝21.7Hz),123.22,122.120.23(J＝15.8Hz),118.06,117.08,23.54(J＝20.4Hz).
2- (4-methoxyphenyl) -6-phenylpyridine
Figure BDA0003048106460000302
White solid, mp.128-130 ℃.1H NMR (500mhz, cdcl3) δ 8.19-8.12 (m, 1H), 7.78 (t, J =7.8hz, 0h), 7.64 (dd, J =7.7,3.3hz, 1h), 7.51 (t, J =7.5hz, 1h), 7.44 (t, J =7.3hz, 0h), 7.04 (d, J =8.8hz, 1h), 3.88 (s, 3H); 13C NMR (125MHz, CDCl3) delta 159.46,155.58,155.40,138.50,136.38,131.04,127.87,127.61,127.22,125.93,116.91,116.84,113.00,54.30.
2- (4-chlorophenyl) -6-phenylpyridine
Figure BDA0003048106460000303
Light yellow solid, mp.125-127 ℃; 1 H NMR(500MHz,CDCl 3 )δ8.19–8.07(m,4H),7.81(d,J＝7.8Hz,1H),7.74–7.64(m,2H),7.53–7.43(m,5H)； 13 C NMR(125MHz,CDCl 3 )δ157.16,155.78,139.48,138.09,135.27,132.53,131.11,129.05,128.44,127.17,119.10,118

Claims (6)

1. the pincer-like manganese complex is characterized by having a structural formula as follows:
Figure DEST_PATH_IMAGE002
wherein, X - Is Br - ，Cl - ，I - Or F - Y is NR 1 R 2 、SR 3 Or PR 4 R 5 Said R is 1 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; said R is 2 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; the R is 3 Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, phenyl, methyl-substituted phenyl, ethyl-substituted phenyl or propyl-substituted phenyl; the R is 4 Is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, or propyl-substituted phenyl; the R is 5 Is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, or propyl-substituted phenyl.
2. The manganese pincer complex according to claim 1, wherein X is - Is Br - Y is NMe 2 ，NEt 2 ，N i- Pr 2 SEt, SPh orPPh 2 。
3. The method for preparing the pincer-shaped manganese complex according to claim 2, wherein the compound shown in the formula II and the compound shown in the formula III are reacted to obtain the pincer-shaped manganese complex shown in the formula I,
Figure DEST_PATH_IMAGE004
wherein Y is NMe 2 ，NEt 2 ，N i- Pr 2 SEt, SPh or PPh 2 。
4. A catalyst composition comprising an active ingredient and an auxiliary, wherein the active ingredient is the pincer-shaped manganese complex according to claim 1.
5. The catalyst composition of claim 4 wherein the promoter ist-BuOK、t-BuONa、i-PrONa、EtONa、MeONa、KOH、NaOH、NaHBEt 3 、K 2 CO 3 、Na 2 CO 3 One or more combinations thereof.
6. Use of the pincer-like manganese complex of claim 1 or the catalyst composition of claim 4 or 5 for the preparation of quinoline or pyridine derivatives by the dehydrogenation coupling of o-amino aryl alcohols or γ -amino alcohols, ketones or secondary alcohols.
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