CN114181090B - Preparation method for synthesizing amine compound by co-catalyzing hydrosilation of amide through iridium and boron reagent - Google Patents

Preparation method for synthesizing amine compound by co-catalyzing hydrosilation of amide through iridium and boron reagent Download PDF

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CN114181090B
CN114181090B CN202010969949.8A CN202010969949A CN114181090B CN 114181090 B CN114181090 B CN 114181090B CN 202010969949 A CN202010969949 A CN 202010969949A CN 114181090 B CN114181090 B CN 114181090B
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黄培强
韩丰
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Abstract

The preparation method for synthesizing the amine compound by the co-catalysis of the amide through the iridium and the boron reagent comprises the following steps: in an organic solvent, reacting amide and silane under the catalysis of an iridium complex and a boron reagent, and then concentrating and purifying to obtain amine; the molar ratio of the amide to iridium complex to the boron reagent to the silane is 1:0.0001-0.001:0.01-0.05:2-4; the method takes stable and easily available amide as a raw material, and uses the iridium complex with very low catalyst loading to co-catalyze hydrosilation with the boron reagent to synthesize the amine compound with high efficiency. The method has the advantages of simple operation and separation of each step, high reaction rate, mild reaction conditions, low-cost and easily-obtained commercial reagents, high yield and good functional group tolerance.

Description

Preparation method for synthesizing amine compound by co-catalyzing hydrosilation of amide through iridium and boron reagent
Technical Field
The invention relates to the field of preparation of amine compounds, in particular to a preparation method for synthesizing amine compounds by co-catalyzing hydrosilation of amide with iridium and a boron reagent.
Background
Amine is often an important structural unit in natural products and drug molecules with biological activity, such as novel antidepressant, escitalopram (2.1 and Clomipramine) (Clomipramine, 2.5), atypical antipsychotic, aripiprazole (2.2 and quinolone antibacterial, levofloxacin (2.3), fenpipril (fenpipride, 2.4) for treating chronic bronchitis and respiratory insufficiency, and Diltiazem (2.6) as a calcium ion blocker.
Figure BDA0002682736360000011
Amine compounds have wide application in the fields of medicine, pesticides and the like, and a plurality of methods are developed for preparing amine at present. The conventional synthesis method of amine refers to a general method of synthesizing an amine compound by heating (or high pressure) with a conventional heater in the presence of a catalyst, and several amine synthesis methods are described below.
The nitro compound is synthesized into amine through chemical reduction or catalytic hydrogenation, and the chemical reduction is divided into metal reduction and metal hydride reduction.
Reductive amination is a simple method of converting an aldehyde ketone to an amine. Reductive amination of aldehyde ketones can be divided into two steps, first dehydration of carbonyl amine to form imine (Schiff base), followed by reduction to amine via sodium borohydride or sodium cyanoborohydride.
The reduction of nitrile groups to primary amines is relatively easy and the process for preparing primary amines by hydrogenation of cyano groups is well established, and many catalysts are available for catalyzing the hydrogenation reduction of nitrile, such as platinum oxide, nickel, palladium, cobalt and nickel boride.
Reduction of the azide, the azide can be conveniently introduced into the organic molecule by means of an inorganic azide, mainly by nucleophilic substitution of the halogen (typically bromine) in the molecule, which is then reduced to the amine by means of a suitable reagent. In addition, the amino group may be protected by a suitable reagent under mild conditions upon reduction of the azido group to an amino group. The method can also be used for preparing amine compounds which are not easy to synthesize by other methods.
When the amide without substituent on nitrogen atom is reacted with alkali solution of sodium hypochlorite or sodium hypobromite, the carbonyl is removed to generate primary amine, and the carbon chain is reduced by one carbon atom in the reaction. This is the method of amine production found by huffman, commonly referred to as the huffman degradation reaction.
Amide reduction is one of the important reactions in organic synthesis and is also a common method for synthesizing amines. By selecting appropriate reaction conditions, amides (including lactams) can be reduced to various target products such as aldehydes, alcohols, imines, or amines, with the reduction of amides to amines being of paramount importance. Traditional methods for the reduction of amides to amines require multiple steps. For example, first with Lawesson's reagent or P 4 S 10 The amide is prepared into thioamide, and then the amide is reduced into amine through two steps by desulfurization with Ni reagent.
Figure BDA0002682736360000021
In the last decade, many metals such as Mo, ru, co, rh, ir, os, pt, in, ti, mn, etc. have been developed for catalytic direct reduction, but all have little practical application value due to the poor availability of catalysts or the harsh reaction conditions.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation method for synthesizing an amine compound by co-catalyzing hydrosilation of amide by iridium and a boron reagent, which is to take stable and easily available amide as a raw material, and synthesize the amine compound in high yield by co-catalyzing hydrosilation reaction of an iridium complex and the boron reagent.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method for synthesizing the amine compound by the co-catalysis of the amide through the iridium and the boron reagent comprises the following steps: in an organic solvent, reacting amide and silane under the catalysis of an iridium complex and a boron reagent, and then concentrating and purifying to obtain amine; the synthetic route is as follows:
Figure BDA0002682736360000022
wherein R is 1 And R is 2 Selected from hydrogen, alkyl or aryl; r is R 3 Selected from hydrogen, alkyl, aryl or alkoxy；[Ir]Is iridium complex, [ B ]]Is a boron reagent and Si-H is silane.
The alkyl is selected from C1-C20 alkyl, the aryl is selected from C6-C20 aryl, and the alkoxy is selected from C1-C7 alkoxy.
In the invention, the molar ratio of the amide to the iridium complex to the boron reagent to the silane is 1:0.0001-0.001:0.01-0.05:2-4.
The iridium complex comprises IrCl (CO) (PPh 3 ) 2 。
The boron reagent comprises (C) 6 F 5 ) 3 B (trifluorophenyl boron).
The silane is selected from alkoxysilanes or alkylsilanes, e.g. (EtO) 3 SiH (triethoxysilane), et 3 SiH (triethylsilane), PMHS (polymethylhydrosilane), TMDS (1, 3-tetramethyldisiloxane), et 2 SiH 2 (Diethylsilane) or Ph 2 SiH 2 (diphenylsilane), and the like.
The organic solvent is selected from ether, halogenated hydrocarbon or aromatic hydrocarbon. The ether is selected from C2-C6 ethers, and the halogenated hydrocarbon is selected from C1-C6 halogenated hydrocarbons. Preferably, the organic solvent is selected from tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, dichloroethane, toluene or xylene.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the method takes stable and easily available amide as a raw material, and uses the iridium complex with very low catalyst loading to co-catalyze hydrosilation with the boron reagent to synthesize the amine compound with high efficiency. The method has the advantages of simple operation and separation of each step, high reaction rate, mild reaction conditions, low-cost and easily-obtained commercial reagents, high yield and good functional group tolerance.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and apparent, the invention is further described in detail below with reference to the embodiments.
Example 1
Synthesis of N-methyl-N- (2-naphthyl) aniline (a)
Figure BDA0002682736360000031
N-methyl-N-phenyl-2-naphthamide (261 mg) was dissolved in toluene, and iridium complex [ IrCl (CO) (PPh) was added in this order at room temperature 3 ) 2 ](8 mg), silane TMDS (1, 3-tetramethyldisiloxane) (0.36 mL) and B (C 6 F 5 ) 3 (15 mg). After stirring the reaction, it was concentrated and purified to give a white solid a (240 mg, yield 97%). IR (film) v max :3052,2962,2819,1598,1505,1367,1119,939,812,747cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ3.02(s,3H),4.63(s,2H),6.66-6.83(m,2H),7.17-7.28(m,2H),7.30-7.50(m,3H),7.60-7.69(m,1H),7.71-7.85(m,3H)ppm； 13 C NMR(100MHz,CDCl 3 )δ38.6,57.1,112.5,112.6,116.8,125.2,125.3,125.6,126.2,127.7,128.4,129.3,132.8,133.6,136.7,149.9ppm；MS(ESI,m/z):247(M+H + )。
Example 2
Synthesis of 1-Benzylazepan (b)
Figure BDA0002682736360000041
1-Benzylazepin-2-one (203 mg) was dissolved in tetrahydrofuran, and iridium complex [ IrCl (CO) (PPh) was added sequentially at room temperature 3 ) 2 ](8mg，1mol％)，B(C 6 F 5 ) 3 (15 mg) and silane TMDS (1, 3-tetramethyldisiloxane) (0.36 mL). After the reaction was stirred and concentrated, colorless liquid b (168 mg, yield 89%) was obtained. IR (film) v max :3021,2921,2847,2979,1490,1453,1353cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ1.67(s,8H),2.68(s,4H),3.69(s,2H),7.21-7.49(m,5H)ppm； 13 C NMR(100MHz,CDCl 3 )δ27.0,28.2,55.6,62.7,126.6,128.0,128.7,140.0ppm；MS(ESI,m/z):189.4(M+H + )。
Example 3
Synthesis of naftifine (c)
Figure BDA0002682736360000042
N-methyl-N- (1-naphthylmethyl) cinnamamide (301 mg) was dissolved in toluene, and iridium complex [ IrCl (CO) (PPh) was added sequentially at room temperature 3 ) 2 ](8 mg,1 mol%), TMDS (0.36 mL) and B (C) 6 F 5 ) 3 (15 mg). The reaction was concentrated under stirring, and purified to give pale yellow liquid c (178 mg, yield 62%). IR (film) v max :3022,2985,2782,1494,1369,1065cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ2.27(s,3H),3.27(dd,J＝6.6,1.1Hz,2H),3.94(s,2H),6.36(dt,J＝15.9,6.6Hz,1H),6.56(d,J＝15.9Hz,1H),7.24-7.17(m,1H),7.33-7.27(m,2H),7.55-7.35(m,6H),7.76(d,J＝8.0Hz,1H),7.83(dd,J＝8.3,1.0Hz,1H),8.30(d,J＝8.4Hz,1H)ppm； 13 C NMR(100MHz,CDCl 3 )δ42.4,60.0,60.4,124.6,125.1,125.5,125.9,126.3,127.3,127.4,127.5,127.9,128.4,128.5,132.4,132.6,133.8,134.8,137.1ppm；MS(ESI,m/z):287.1(M+H + )。
Example 4
Synthesis of Tribenzylamine (d)
Figure BDA0002682736360000051
N, N-dibenzylbenzamide (301 mg) was dissolved in toluene, and iridium complex [ IrCl (CO) (PPh) was added sequentially at room temperature 3 ) 2 ](0.08 mg,0.01 mol%) silane TMDS (0.36 mL) and B (C) 6 F 5 ) 3 (15 mg). After stirring the reaction, it was concentrated and purified to give pale yellow liquid d (281 mg, yield 98%). IR (film) v max :3082,3062,3028,2925,2881,2837,2802,1603,1493,1452,1366,1247,1122,1028cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ3.55(s,6H),7.18-7.26(m,3H),7.26-7.35(m,6H),7.37-7.43(m,6H)ppm； 13 C NMR(100MHz,CDCl 3 )δ57.9,126.9,128.2,128.8,139.7ppm；MS(ESI,m/z):288.3(M+H + ).
Example 5
Synthesis of N, N-dibenzyl hexadecylamine (e)
Figure BDA0002682736360000052
N, N-dibenzyl palmitamide (435 mg) was dissolved in toluene, and iridium complex [ IrCl (CO) (PPh) was added at room temperature in this order 3 ) 2 ](0.08 mg,0.01 mol%) silane TMDS (0.36 mL) and B (C) 6 F 5 ) 3 (15 mg. Concentrated after stirring, purified to give e (391 mg, 93% yield) IR (film) v as a pale yellow liquid max :3085,3027,3026,2924,2793,1601,1453,1365,1259,1074,743,697cm -1 ； 1 H NMR(500MHz,CDCl 3 )δ0.87(t,J＝7.1Hz,3H),1.16-1.32(m,26H),1.45-1.53(m,2H),2.38(t,J＝7.2Hz,2H),3.53(s,4H),7.16-7.20(m,2H),7.26-7.29(m,4H),7.34-7.35(m,4H)ppm； 13 C NMR(125MHz,CDCl 3 )δ14.1,22.7,27.0,27.3,29.4,29.5,29.7(2C),29.70(2C),29.73(4C),31.95,53.42,58.3,126.7,128.1,128.7,140.1ppm；HRMS-ESI calcd for[C 30 H 48 N] + (M+H + ):422.3781；found:422.3784.
Example 6
Synthesis of dibenzylamine (f)
Figure BDA0002682736360000053
N-Benzylbenzamide (211 mg) was dissolved in toluene, and Iridium complex [ IrCl (CO) (PPh) was added in this order at room temperature 3 ) 2 ](8 mg,1 mol%), silane TMDS (0.36 mL) and B (C) 6 F 5 ) 3 (30 mg). After stirring the reaction, it was concentrated and purified to give f (63 mg, yield 32%) as a pale yellow liquid. IR (film) v max :3332,3083,3061,3024,2917,2817,1494,1452,1109,1027cm -1 ； 1 H NMR(400MHz,CDCl 3 )δ1.68(s,1H),3.80(s,4H),7.19-7.40(m,10H)ppm； 13 C NMR(100MHz,CDCl 3 )δ53.2,127.0,128.2,128.4,140.4ppm；MS(ESI,m/z):198(M+H + ).

Claims (5)

1. The preparation method for synthesizing the amine compound by the co-catalysis of the amide through the iridium and the boron reagent is characterized by comprising the following steps: in an organic solvent, reacting amide and silane under the catalysis of an iridium complex and a boron reagent, and then concentrating and purifying to obtain amine; the synthetic route is as follows:
Figure FDA0004136787470000011
wherein R is 1 And R is 2 Selected from hydrogen, alkyl or aryl; r is R 3 Selected from hydrogen, alkyl, aryl; [ Ir ]]Is iridium complex, [ B ]]For boron reagent, si-H is a silane selected from (EtO) 3 SiH, PMHS, or 1, 3-tetramethyldisiloxane;
the molar ratio of the amide to iridium complex to the boron reagent to the silane is 1:0.0001-0.001:0.01-0.05:2-4;
the iridium complex adopts IrCl (CO) (PPh 3 ) 2 ；
The boron reagent adopts (C) 6 F 5 ) 3 B。
2. The method for synthesizing an amine compound from amide through co-catalytic hydrosilation with iridium and boron reagents according to claim 1, wherein the method comprises the following steps: the alkyl is selected from C1-C20 alkyl, and the aryl is selected from C6-C20 aryl.
3. The method for synthesizing an amine compound from amide through co-catalytic hydrosilation with iridium and boron reagents according to claim 1, wherein the method comprises the following steps: the organic solvent is selected from ether, halogenated hydrocarbon or aromatic hydrocarbon.
4. The method for synthesizing an amine compound from amide through co-catalytic hydrosilation with iridium and boron reagents according to claim 3, wherein the method comprises the following steps: the ether is selected from C2-C6 ethers, and the halogenated hydrocarbon is selected from C1-C6 halogenated hydrocarbons.
5. The method for synthesizing an amine compound from amide through co-catalytic hydrosilation with iridium and boron reagents according to claim 3, wherein the method comprises the following steps: the organic solvent is selected from tetrahydrofuran, 2-methyltetrahydrofuran, methylene dichloride, dichloroethane, toluene or xylene.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484385A (en) * 2019-01-28 2020-08-04 中国科学院上海有机化学研究所 Hydrosilylation reaction method for catalyzing amide by organic boron and inorganic base

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111484385A (en) * 2019-01-28 2020-08-04 中国科学院上海有机化学研究所 Hydrosilylation reaction method for catalyzing amide by organic boron and inorganic base

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Efficient and selective hydrosilylation of secondary and tertiary amides using an iridium(III) metallacycle catalyst: development and mechanistic investigation;Yann Corre等;《ChemCatChem》;20170306;第9卷(第11期);2009-2017，尤其是table1以及table3 *
Metal-Free Reduction of Secondary and Tertiary N‑Phenyl Amides by Tris(pentafluorophenyl)boron-Catalyzed Hydrosilylation;Ryan C. Chadwick等;《J. Org. Chem. 》;20140717;第79卷(第16期);7728-7733，尤其是第7729页table1 entry7 *
Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium-Catalyzed Hydrosilylation and Single Electron Transfer Strategy;Tatiana Rogova等;《ACS Catal.》;20200827;第10卷(第19期);11438-11447 *

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