Catalytic stereoselective Mannich reaction under solvent-free conditions

Najmadin Azizi; Roya Baghi; Elham Batebi; Seyed Mohammad Bolourtchian

doi:10.1016/j.crci.2011.10.011

Catalytic stereoselective Mannich reaction under solvent-free conditions

Najmadin Azizi ¹ ; Roya Baghi ¹ ; Elham Batebi ¹ ; Seyed Mohammad Bolourtchian ¹

¹ Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran, Iran

Comptes Rendus. Chimie, Volume 15 (2012) no. 4, pp. 278-282.

Résumé

Silicon tetrachloride catalyzed one-pot three-component Mannich reaction of cyclic ketones, aromatic aldehydes, and aromatic amine under solvent-free conditions affords the corresponding β-amino ketones with excellent yield and good to excellent anti-selectivity.

Métadonnées

Reçu le : 2011-09-11
Accepté le : 2011-10-24
Publié le : 2011-12-12

DOI : 10.1016/j.crci.2011.10.011

Mots clés : Amine, Aldehyde, β-amino ketone, Mannich reaction, Solvent-free, Silicon tetrachloride

Affiliations des auteurs :

Najmadin Azizi ¹ ; Roya Baghi ¹ ; Elham Batebi ¹ ; Seyed Mohammad Bolourtchian ¹

¹ Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran, Iran

@article{CRCHIM_2012__15_4_278_0,
     author = {Najmadin Azizi and Roya Baghi and Elham Batebi and Seyed Mohammad Bolourtchian},
     title = {Catalytic stereoselective {Mannich} reaction under solvent-free conditions},
     journal = {Comptes Rendus. Chimie},
     pages = {278--282},
     publisher = {Elsevier},
     volume = {15},
     number = {4},
     year = {2012},
     doi = {10.1016/j.crci.2011.10.011},
     language = {en},
}

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AU  - Seyed Mohammad Bolourtchian
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JO  - Comptes Rendus. Chimie
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EP  - 282
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PB  - Elsevier
DO  - 10.1016/j.crci.2011.10.011
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%0 Journal Article
%A Najmadin Azizi
%A Roya Baghi
%A Elham Batebi
%A Seyed Mohammad Bolourtchian
%T Catalytic stereoselective Mannich reaction under solvent-free conditions
%J Comptes Rendus. Chimie
%D 2012
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Najmadin Azizi; Roya Baghi; Elham Batebi; Seyed Mohammad Bolourtchian. Catalytic stereoselective Mannich reaction under solvent-free conditions. Comptes Rendus. Chimie, Volume 15 (2012) no. 4, pp. 278-282. doi : 10.1016/j.crci.2011.10.011. https://comptes-rendus.academie-sciences.fr/chimie/articles/10.1016/j.crci.2011.10.011/

Version originale du texte intégral

1 Introduction

The classical Mannich reaction, in which an aminomethyl group is introduced to the α position of a carbonyl function, provides useful routes for the synthesis of β-amino ketones and esters, which are versatile building blocks for the preparation of many nitrogen-containing biologically important compounds [1–4].

Recently, a three-component approach for this reaction using organocatalyst and other catalysts, with in situ formation of imines, has gained considerable importance as it allows structural variations. Accordingly, several recent reports of catalytic Mannich reaction using known organocatalyses [5–7], proline [8–11], siloxy serine [12], adenine [13], Trypsin [14], p-dodecyl benzenesulphonic acid (DBSA) [15,16], ionic liquid [17–20], Zn(OTf)₂ [21], Silica-supported aluminum chloride [22], ZrOCl₂·8H₂O [23], Bismuth Triflate [24–26], cationic organobismuth complex [27], HCl/SDS [28], boric acid and glycerol [29], HBF₄ [30], Zn(proline)₂ [31], ceric ammonium nitrate [32], heteropoly acid [33], WO_x–ZrO₂ [34], polyaniline salts [35], Fe(Cp)₂PF₆[36], DDQ [37], ZnCl₂/SiO₂ [38], SO₄²⁻/TiO₂ [39], TiCl₄/PhSiCl₃ [40,41], perchloric acid in Triton X10 [42], ZnI₂ [43], 2-pyrrolidinecarboxylic acid ionic liquid [44], chiral Brønsted acid [45], are found in the literature.

However, the yields obtained were only moderate, even with high catalyst loadings and regardless of the immense importance of this reaction, only a few diastereoselective α-aminomethylation reactions have been developed (Table 1). Thus, expanding the scope of Lewis acid catalysis under solvent-free condition in a one-pot three-component Mannich reaction is a useful and challenging objective. In this context, we wish to report a simple version of an environmentally benign Mannich reaction with different aromatic aldehydes, cyclic ketones and aromatic amines for the synthesis of β-amino carbonyl compounds under solvent-free condition in presence of SiCl₄ as catalyst with good yield and excellent selectivity as shown in Scheme 1.

Entry	Catalyst	Mol %	Solvent	Yields	Anti:syn	Ref.
1	Ln(OTf)₃	2	Water	88	92:8	[28]
2	HCl/SDS	10	Water	83	94:6	[28]
3	HBF₄/SDS	10	Water	91	97:3	[28]
4	ZnCl₂/SiO₂	1	Neat	97	85:15	[38]
5	Fe(Cp)₂PF₆	5	Neat	94	76:24	[36]
6	WO_x–ZrO₂	50 (mg)	Neat	90	80:20	[34]
7	Ionic liqiud	10	Water	83	75:25	[20]
8	Bismuth triflate	5	Water	84	86:14	[26]
9	H₃MoW₁₂O₄₀	0.12	Water	84	63:37	[33]
10	ZrOCl₂·8H₂O	15	Neat	92	99:1	[23]
11	DBSA	1	Water	100	70:30	[16]
12	HClO₄/TX10	10	Water	92	76:24	[42]
13	ZnI₂	1	Neat	95	64:36	[43]
14	Boric acid	10	Water	80	36:64	[29]
15	Adenine/H₂O₂	20	Water	95	83:17	[13]
16	Siloxy serine	20	Water	82	81:19	[12]
17	Organobismuth	5	Water	98	95:5	[27]
18	SiCl₄	2	Neat	97	100:00	–

Scheme 1
Optimization of reaction condition.

2 Experimental

2.1 General

All chemicals were obtained from commercial suppliers and used as supplied. NMR spectra were recorded on a Bruker ACF 500 using CDCl₃/CCl₄ or CDCl₃/DMSO-d₆ as solvent. Column chromatography was performed on silica gel, Merck grade 60. Melting points were recorded on Buchi 535 melting point apparatus and are uncorrected. Ethyl acetate, hexane, diethyl ether, ethanol and water were distilled prior to use. Reactions were carried out at room temperature and all aldehydes, ketones, amines and catalyst employed are commercially available.

2.2 General procedure

To the mixture of cyclic ketones (cyclohexanone or cyclohepatone, 3 mmol, and tetrahydro-4H-pyran-4-one, 1.5 mmol), aromatic aldehyde (1 mmol) and aromatic amine (1 mmol) in the test tube, SiCl₄ (2 mol %) was added. The mixture was stirred at room temperature for appropriate time until the reaction mixture was solidified. To the crude product, diethyl ether or ethyl acetate (10 ml) was added and washed with saturated aqueous sodium chloride (5 mL) and water (10 mL). The organic layer was dried over anhydrous Mg₂SO₄ and solvent was evaporated under vacuum (rotary evaporator). The oily products were subjected to column chromatography over silica gel (230–400) with ethyl acetate:hexane (2:8) as eluent. The solid products were crystallized directly from ethanol and some cases with diethyl ether. All compounds were known and characterized on the basis of their spectroscopic data (¹H NMR, and m.p.) and by comparison with those reported in the literature.

3 Results and discussion

With the increasing interest in developing environmentally benign reactions, the atom-economic catalytic process that employs unmodified ketones, aromatic amine, and aromatic aldehyde would be an ideal Mannich-type reaction, and is attracting more attention. In continuation of our studies on the new variants, of one-pot, three-component Mannich type reaction, and our ongoing program for developing green organic reactions by using water as reaction medium or by performing organic transformations under solvent-free conditions [33,46–48]. Herein, we report, direct three-component anti-selective Mannich reactions promoted by silicon tetrachloride under solvent-free condition. First, the three-component Mannich reaction of benzaldehyde, aniline, and cyclohexanone were selected as a model. As a preliminary study, reaction temperature and solvents were screened in the model reaction. The results of extensive solvent screening and optimization are shown in Scheme 1. SiCl₄ catalyzed Mannich reactions in organic solvents such as ether, dichloromethane, methanol, and ethanol led to recovery of starting material and imines in addition to small amounts of the desired products 4 in low yield. Among the screened reaction solvent systems, solvent-free conditions (neat) was the ideal reaction media, since in this condition, the Mannich-type reactions proceed smoothly and afford the desired adducts in excellent yield and excellent anti-selectivity. Solvent-free organic reactions would be faster and more selective, leading to more favorable kinetics. Furthermore, no Mannich base could be detected when a mixture of benzaldehyde, aniline and cyclohexanone was stirred for 12 h in the absence of silicon tetrachloride, which indicated that the catalyst should be absolutely necessary for the Mannich reaction (Scheme 1).

Then, the scope of the SiCl₄ catalyzed Mannich-type reaction of other aromatic aldehydes (1), aromatic amines (2) and ketones (3) were investigated under the optimized reaction conditions (Table 2). In general, the reaction proceeded smoothly at room temperature to give the corresponding products in reasonable to good yields ranged from 70 to 97%. At the beginning, we made a search for the aryl-aldehyde substrate scope with aniline and cyclohexanone as model substrates and the results are shown in Table 2. Generally, excellent yields of β-amino ketones were obtained under optimized reaction conditions with aromatic aldehydes as well as heterocyclic aldehydes. This reaction worked well for a variety of aldehydes including those bearing an electron-withdrawing group, and the corresponding β-amino ketones were obtained with excellent yields. Several electron-rich aromatic aldehydes lead to the desired products in good yields, too. The scope of our method was extended to other amines. In the case of amines having an electron-donating group, such as 4-isopropyl aniline, the corresponding amino alcohols was obtained in good yields. Furthermore, amines with electron-withdrawing groups, such as 4-chloroaniline and 3,4-dichloroaniline, gave the desired product in good yields. However, there is not any relationship between electronic effects and stereoselectivity of this reaction.

Entry	Ar	Ar’	Z	Syn: Anti	Yield^a,b (%)	Ref.
1	C₆H₅	C₆H₅	CH₂	00:100	97	[33]
2	C₆H₅	C₆H₅	O	10:90	92	[45]
3	4-ClC₆H₄	C₆H₅	CH₂	00:100	92	[19]
4	4-ClC₆H₄	C₆H₅	O	15:85	82	[39]
5	4-BrC₆H₄	C₆H₅	CH₂	00:100	88	[33]
6	3-ClC₆H₄	C₆H₅	CH₂	10:88	78	[19]
7	C₆H₅	3-CH₃C₆H₄	CH₂	00:100	86	[34]
8	C₆H₅	3-CH₃C₆H₄	O	20:80	84	[45]
9	4-BrC₆H₄	2-CH₃C₆H₄	CH₂	13:87	80	[36]
10	4-ClC₆H₄	4-ClC₆H₄	CH₂	25:75	70	[34]
11	C₆H₅	4-OCH₃C₆H₄	CH₂	7:93	82	[34]
12	C₆H₅	4-(CH₃)₂CHC₆H₄	CH₂	21:79	82	[33]
13	4-BrC₆H₄	4-OCH₃C₆H₄	CH₂	13:87	85	[35]
14	C₆H₅	4-BuC₆H₄	CH₂	23:77	83	[33]
15	4-ClC₆H₄	4-BuC₆H₄	CH₂	15:85	78	[44]
16	4-CH₃C₆H₄	C₆H₅	O	8:92	95	[45]
17	4-Pyridyl	C₆H₅	CH₂	10:90	92	[33]
18	4-Pyridyl	C₆H₅	O	12:88	88	[45]
19	3-BrC₆H₄	C₆H₅	CH₂	14:86	80	[33]
20	3-OCH₃C₆H₄	C₆H₅	O	15:85	80	[45]
21	2-Thienyl	C₆H₅	CH₂	12:88	90	[44]
22	2-Thienyl	3-CH₃C₆H₄	CH₂	20:80	72	[19]

^a Isolated yields.

^b Reaction conditions: aromatic aldehyde (1 mmol) and aromatic amine (1 mmol) cyclohexanone, (3 mmol), and tetrahydro-4H-pyran-4-one, (1.5 mmol), SiCl₄ (2 mol %).

In addition, besides the cyclohexanone, cycloheptanone and tetrahydro-4H-pyran-4-one could also be employed to give good yields. However, in case of cycloheptanone as substrate the anti-selectivity is lower than that of cyclohexanone and, this procedure could not afford the corresponding single Mannich base (Table 3).

Entry	Ar’	Ar	Syn:Anti	Yield^a,b (%)	Ref.
1	C₆H₅	C₆H₅	05:95	91	[23]
2	C₆H₅	3-CH₃C₆H₄	24:76	82	[23]
3	4-ClC₆H₄	C₆H₅	19:81	70	[23]
4	4-ClC₆H₄	4-(CH₃)₂CHC₆H₄	24:76	74	[16]
5	C₆H₅	4-MeC₆H₄	15:85	86	[39]
6	4-CH₃C₆H₄	3-ClC₆H₄	10:90	90	[16]

^a Isolated yields.

^b Reaction condition: aromatic aldehyde (1 mmol) and aromatic amine (1 mmol), cyclohepatone (3 mmol) and SiCl₄ (2 mol%).

In general, the anti-products were invariably formed in a major scale, dependent of the nature of substituents on the aldehyde and amines as depicted in Table 2. It is worth mentioning that the aliphatic aldehydes and aliphatic amines were inactive and failed to furnish the desired products with this protocol (Table 4).

Entry	Catalyst	Yield (%)^a 3	Yield (%) 4	Anti:Syn
1	10 μl HCl (32%)	40	50	72:18
2	100 μl HCl (32%)	55	35	85:15
3	2 mL HCl (32%)	5	80	–
4	1 mL HCl (1 M)	60	35	85:15
5	HCl (g)^b,c	5	20	–

^a NMR yields.

^b Anilinium chloride (70%) and benzaldehyde were recovered.

^c HCl gas was prepared by the reaction of concentrated sulfuric acid and sodium chloride.

Differentiation between aromatic aldehyde (cross-aldol condensation) and imine (Mannich reaction) in the competitive reactions is an important task in organic synthesis and in fact, only Mannich reaction product was obtained in this reaction media, which demonstrated that the reaction catalyzed by silicon mentioned above had a good chemoselectivity (Scheme 2) [49–51].

The structures of all the synthesized compounds were established on the basis of their spectroscopic data. The anti- and syn-isomers were identified by the coupling constants (J) of the vicinal protons adjacent to C=O and NH in their ¹H NMR spectra. The anti isomer showed a doublet at δ 4.54 due to CH and the coupling constant J = 7.6 Hz in the ¹H NMR spectrum.

In summary, silicon tetrachloride was found to be a highly efficient catalyst for one-pot three-component Mannich reaction under solvent-free conditions. The procedure provides several advantages, such as mild conditions, high yields, and good to excellent stereoselectivities, shorter reaction time and clear reaction profile.

Acknowledgment

Financial support of this work by Chemistry and Chemical Research Center of Iran is gratefully appreciated.

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