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Article

Silver(I)-Catalyzed C4-H Amination of 1-Naphthylamine Derivatives with Azodicarboxylates at Room Temperature

by
Yuxue Zhang
†,
Mengxue Pei
†,
Fan Yang
* and
Yangjie Wu
College of Chemistry, Green Catalysis Center, Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, China
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Catalysts 2022, 12(9), 1006; https://doi.org/10.3390/catal12091006
Submission received: 18 August 2022 / Revised: 27 August 2022 / Accepted: 30 August 2022 / Published: 6 September 2022
(This article belongs to the Special Issue Advances in Transition Metal Catalysis)
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Versions Notes

Abstract

:
A highly facile and efficient protocol for silver(I)-catalyzed C4–H amination of 1-naphthylamine derivatives with readily available azodicarboxylates utilizing picolinamide as a bidentate directing group is reported, providing an alternative strategy for the synthesis of 4-aminated 1-naphthylamine derivatives. The reaction proceeded smoothly in acetone at room temperature undergoing a self-redox process under the base and external oxidant-free conditions, affording the desired products with good to excellent yields.

Graphical Abstract

1. Introduction

Arylamine compounds are important structural fragments in pharmaceuticals, agrochemicals, dyes, herbicides, and functionalized materials [1,2,3]. Therefore, the development of efficient methods for C-N bond construction have captured much attention. However, traditional synthesis methods usually use pre-functionalized substrates as raw materials to achieve the synthesis of target products, which will increase the cost of reaction synthesis and the complexity of experimental operations [4,5].
In the past few decades, the transition metal-catalyzed C-H functionalization has emerged as a reliable tool in organic synthesis [6,7,8,9,10,11,12]. Therefore, direct oxidative cross-dehydrogenative-coupling (CDC) amination of hydrocarbons with amines has gradually become a fascinating protocol for the C-N bond-forming reaction due to its atom- and step-economy. In 2005, Daugulis’ group introduced a type of picolinamide (PA) moiety as a directing group to complete the C-H activation process, [13] and then, a series of reports for C2-H [14,15,16,17,18,19,20,21] and C8-H [22,23,24,25,26,27,28,29] functionalization reactions of 1-naphthylamine derivatives started to appear. Remarkably, different kinds of C4-H functionalization of 1-naphthylamides derivatives were developed, such as sulfonylation, [30,31,32] amination, [33,34,35,36,37] esterification, [38,39] etherification [40]. Among them, the traditional transition metal-catalyzed amination reaction of 1-naphthylamine derivatives at the C4 site usually utilizes a stoichiometric amount of base and oxidant under heated conditions, and the reaction cost is relatively higher (Scheme 1a).
In recent years, the research interest in our group has mainly focused on the regioselective C-H functionalization of arene compounds with the assistance of the bidentate directing group, such as the direct C-H functionalization of 1-naphthylamine derivatives [24,29,31,33,36,37] and 8-aminoquinoline derivatives [41,42,43,44]. Especially in 2018, our research group reported the reaction of 1-naphthylamine derivatives and azodicarboxylates and successfully realized the C4-H bond amination of the 1-naphthylamine derivative [33]. In this work, we would like to report a facile and efficient protocol for the C4−H amination of 1-naphthylamine derivatives with azodicarboxylates at room temperature under base and oxidant-free conditions (Scheme 1b).

2. Results and Discussion

Initially, N-(naphthalen-1-yl) picolinamide (1a) and diisopropyl azodicarboxylate (DIAD, 2a) was explored as the template reaction substrates for the C4−H amination of 1-naphthylamine derivatives (Table 1 and Tables S1–S3 in Supplementary Materials), and the amination proceeded smoothly in DCE at room temperature in the presence of Ag2O (10 mol%), resulting in the product 3aa in an 80% isolated yield (Table 1, entry 1). The reaction solvents were then examined, and the results showed that acetone was the best solvent with a high yield of 97% (Table 1, entries 2–6). Next, some metal catalysts were examined, and none of them could match the catalytic efficiency of Ag2O (Table 1, entries 7–10). Finally, some control experiments were explored. The reaction did not occur in the absence of Ag2O, indicating that Ag2O played an indispensable role in the reaction (Table 1, entry 11), reducing the reaction time or the catalyst loading results in lower yields of the target product (Table 1, entries 12 and 13).
With the above-optimized reaction conditions, the scope of 1-naphthylamine derivatives was then explored with diisopropyl azodicarboxylate (2a), depicted in Scheme 2. When there was a halogen (F, Cl and Br) substituent at the C3, C4, C5, or C6 position of the pyridine ring of N-(naphthalen-1-yl) picolinamide, the reaction proceeded smoothly to afford the corresponding aminated products in excellent yields (3ba–3ha). In the case of the pyridine ring bearing a methyl substituent at the C3 or C6 position, aminated products were obtained in good yields of 97% and 70%, respectively (3ia and 3ja). These results indicate that the pyridine ring of the 1-naphthylamine derivatives could be compatible with the electron-withdrawing and electron-donating groups. When the naphthalene ring of the substrate possesses an electron-donating group at the C2, C7 or C8 position, the reaction could also proceed smoothly to afford products in moderate to good yields (3ka–3oa). When a quinoline ring was taken instead of the pyridine ring of the substrate, the reaction could generate the corresponding target product in yields in lower yields of 68% (3pa and 3qa). However, when a pyrimidine ring was utilized as a directing group instead of the pyridine ring, the reaction could not occur at all (3ra). These results show that the directing group of 1-naphthylamine derivatives plays an important role in this reaction.
Then, the substrate scope of 1-naphthylamine derivatives with dibenzyl azodicarboxylate(2b) or di-tert-butyl azodicarboxylate (2c) was also screened, and the results are summarized in Scheme 3. The pyridine ring of 1-naphthylamine derivatives could be compatible with functional groups such as halogen atom, methyl and phenyl groups at the C3, C4, C5, or C6 position, leading to the target products in high yields, the results of which are similar to those of Scheme 2. In addition, the naphthalene ring of 1-naphthylamine derivative bearing a phenyl or methyl group at the C8 position reacted with di-tert-butyl azodicarboxylate(2c) could result in the target products in yields of 38% and 83%, respectively (3nc and 3oc).
In order to explore the applicability of this protocol, synthetic applications of the product were demonstrated (Scheme 4). A gram-scale experiment of 1a (0.5000 g) and 2.0 equiv. of diisopropyl azodicarboxylate (2a) proceeded under standard conditions, affording the product 3aa (0.8370 g) with a high yield of 93% (Scheme 4a). Subsequently, some useful transformation of product 3 was pursued such as alkylation and arylation of the naphthyl ring at the C8 position, and bi-functionalized products of 1-naphthylamine derivatives were obtained in moderate yields (Scheme 4b).
In order to explore the reaction mechanism, some control experiments were investigated (Scheme 5). Some designed substrate analogs pending N, O-or N-chelating groups instead of the N, N-bidentate directing group were conducted in this amination reaction, and the products were obtained in low yields or even no products were observed, indicating that the N, N-bidentate directing group is crucial for this reaction (5a–8a). The reaction under a nitrogen and oxygen atmosphere afforded similar yields to that of those performed with air, suggesting that oxygen might not have a very significant effect on this reaction and this reaction might proceed via the self-redox process (Scheme 5b). Then, the 0.2 equiv. radical inhibitor such as 2,2,6,6-tetramethyl-1-piperindinyloxy (TEMPO) or 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the amination reaction, and the product 3aa was obtained in a lower yield; when the loading of TEMPO or BHT increased to 3.0 equiv., the reaction was inhibited successfully; in the presence of BHT under standard conditions, an adduct 9a of BHT with 2a was detected by HRMS (Scheme 5b). These results could imply that the reaction might proceed through a radical process.
On the basis of the above-mentioned obtained results and previous reports of [33,34,35,36,37], a plausible mechanism is proposed as shown in Scheme 6. First, N-(naphthalen-1-yl) picolinamide 1a potentially coordinates with Ag(I) species to afford an aryl-Ag(I) intermediate A, the single electron transfer process of which with Ag(I) species occurs to generate an aryl-Ag(I) intermediate radical B and Ag(0) species. On the other hand, the electrophilic addition of a proton to the azodicarboxylate 2a occurs to generate a nitrogen-centered cation, a redox process of which with the Ag(0) species leads to a nitrogen-centered radical C and active Ag(I) species to fulfill the Ag(I)/Ag(0) catalytic cycle. Subsequently, the electrophilic attack of the nitrogen-centered radicals C to the aryl-Ag(I) intermediate B takes place to afford an aryl-Ag(I) intermediate D. Finally, the intramolecular proton transfer process of the aryl-Ag(I) intermediate D affords the N-Ag(I) coordinated complex E, the ligand dissociation of which would result in the target product 3aa and regenerate catalytically active Ag(I) species to complete the catalytic cycle.
Intermediate B is an open-shell structure with a single unpaired electron distributed in the complex. Mulliken spin densities and singly occupied molecular orbitals (SOMO) are shown in Figure 1. The highest spin density is located on the para-carbon atom C4 (0.36 au), followed by a lower spin density on the ortho-carbon C2 (0.27 au) in the naphthyl ring. A molecular orbital (MO) analysis showed that the SOMO is primarily located on the naphthyl ring with partial contribution from the core region of N-Ag-N of the intermediate B. Among all the carbon atoms in the naphthyl ring, C4 is calculated to be the most-likely reactive site for the attack of the nitrogen racial, which is consistent with experiments.

3. Experimental Section

3.1. General Information

1H and 13C NMR spectra were recorded on a Bruker DPX-400 spectrometer with CDCl3 as the solvent and TMS as an internal standard. Chemical shifts are expressed in parts per million (δ) and the signals were reported as s (singlet), d (doublet), t (triplet), m (multiplet), and coupling constants (J) were given in Hz. Chemical shifts as internal standard were referenced to CDCl3 (δ = 7.26 for 1H and δ = 77.16 for 13C NMR as internal standard). Melting points were measured using a WC-1 microscopic apparatus. High-resolution mass spectra were ensured on an Agilent Technologies 1290–6540 HPLC/Accurate-Mass Quadrupole Time-of-Flight LC/MS. All solvents and chemicals were obtained from commercial sources and used as received without further purification unless otherwise noted.

3.2. General Procedure for Synthesis of Product 3aa

A Schlenk tube was equipped with a magnetic stir bar and charged with N-(naphthalen-1-yl)picolinamide 1a (0.1 mmol), 2a (0.2 mmol, 2 equiv), Ag2O (10 mol%) in acetone (1.0 mL). The resulting mixture was sealed and stirred for 8 h at room temperature. Upon completion, CH2Cl2 (10 mL) was added to the reaction system, and the resulting mixture was filtered through a pad of celite. The filtrate was extracted with H2O (20 mL), and the aqueous layer was extracted with CH2Cl2 (2 × 10 mL). The collected organic layer was dried with anhydrous Na2SO4, filtered and concentrated under vacuum. The residue was purified by column chromatography on silica gel (200–300 mesh) using hexane-EtOAc as eluent (3:1, v/v) to afford the pure product 3aa.

3.3. General Procedure for Synthesis of Product 3

Mixture of 3 (0.1 mmol, 1.0 equiv), Pd(OAc)2 (15 mol%), CH3I or PhI (0.4 mmol, 4.0 equiv), anhydrous KOAc (0.2 mmol, 2.0 equiv), and 1,4-dioxane or xylene (1 mL) was placed in a 25 mL Schlenk tube with a rubber plug under air. The tube was heated at 130 °C for 24 h or 12 h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, filtered through celite, and concentrated in vacuo. The residue was purified by silica gel column chromatography with petroleum ether-ethyl acetate (5:1, v/v) to afford the desired products.

3.4. Spectral Data for Products

3aa. pale yellow solid. (44.0 mg, 97%), Rf = 0.32 (25% EtOAc in hexane), mp 176.9–178.0 °C; 1H NMR (400 MHz, CDCl3) δ 10.82 (s, 1H), 8.71 (d, J = 7.93 Hz, 1H), 8.36 (d, J = 7.93 Hz, 1H), 8.36 (d, J = 7.81 Hz, 1H), 8.12–8.10 (m, 2H), 7.94 (td, J1 = 1.56 Hz, J2 = 7.68 Hz, 1H), 7.75 (s, 1H), 7.63–7.56 (m, 2H), 7.54–7.51 (m, 1H), 7.28 (s, 1H), 5.02–5.01 (m, 2H), 1.25–1.05 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.2, 156.1, 149.8, 148.1, 137.8, 134.9, 132.7, 130.7, 126.9, 126.8, 126.7, 126.5, 126.0, 123.7, 122.5, 120.8, 118.1, 70.9, 70.0, 22.0, 21.8; HRMS (ESI+) m/z [M + H]+ calcd for C24H27N4O5: 451.1976, Found: 451.1977.
3ba. yellow solid (43.6 mg, 93%), Rf = 0.32 (25% EtOAc in hexane), mp 156.5–158.0 °C; 1H NMR (400 MHz, CDCl3) δ 10.55 (s, 1H), 8.53 (d, J = 2.70 Hz, 1H), 8.40–8.37 (m, 2H), 8.09–8.05 (m, 2H), 7.77–7.75 (m, 1H), 7.64–7.54 (m, 3H), 7.36 (s, 1H), 5.05–5.01 (m, 2H), 1.44–1.09 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 161.4 (d, J = 263.43 Hz), 161.2, 156.1, 146.2 (d, J = 3.79 Hz), 136.8 (d, J = 25.40 Hz), 135.1, 132.5, 130.7, 126.8 (d, J = 11.09 Hz), 126.5, 125.9, 124.5, 124.4, 124.3 (d, J = 18.66 Hz), 123.8, 120.7, 118.3, 70.9, 70.0, 22.0; 19F NMR (376 MHz, CDCl3): δ -121.18 (s, 1F); HRMS (ESI+) m/z [M + H]+ calcd for C24H26FN4O5: 469.1882, Found: 469.1881.
3ca. yellow solid (45.0 mg, 93%), Rf = 0.32 (25% EtOAc in hexane), mp 170.9–172.6 oC; 1H NMR (400 MHz, CDCl3) δ 10.57 (s, 1H), 8.64 (d, J = 2.07 Hz, 1H), 8.38 (d, J = 7.97 Hz, 1H), 8.30 (d, J = 8.36 Hz, 1H), 8.09–8.04 (m, 2H), 7.91 (dd, J1 = 2.31 Hz, J2 = 8.37 Hz, 1H), 7.76 (s, 1H), 7.62–7.56 (m, 2H), 7.32 (s, 1H), 5.02–5.01 (m, 2H), 1.43–1.09 (m, 12 H); 13C NMR (100 MHz, CDCl3) δ 161.4, 156.1, 148.0, 147.2, 137.5, 135.5, 135.2, 132.4, 130.7, 126.9, 126.8, 126.2, 125.9, 123.8, 123.6, 120.6, 118.3, 70.9, 70.0, 22.0; HRMS (ESI+) m/z [M + H]+ calcd for C24H26ClN4O5: 485.1586, Found: 485.1584.
3da. yellow solid (50.1 mg, 95%), Rf = 0.32 (25% EtOAc in hexane), mp 139.5–140.5 °C; 1H NMR (400 MHz, CDCl3) δ 10.58 (s, 1H), 8.76 (d, J = 1.96 Hz, 1H), 8.38 (d, J = 7.95 Hz, 1H), 8.24 (d, J = 8.30 Hz, 1H), 8.08–8.04 (m, 3H), 7.75 (s, 1H), 7.62–7.56 (m, 2H), 7.29 (s, 1H), 5.02–5.01 (m, 2H), 1.25–1.09 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 161.5, 156.1, 149.4, 148.3, 140.5, 135.2, 132.4, 130.7, 126.8, 126.8, 126.6, 125.9, 124.5, 124.0, 123.8, 120.6, 118.3, 70.9, 70.0, 22.0; HRMS (ESI+) m/z [M + H]+ calcd for C24H26BrN4O5: 529.1081, Found: 529.1077.
3ea. yellow solid (50.3 mg, 95%), Rf = 0.32 (25% EtOAc in hexane), mp 176.2–178.4 °C; 1H NMR (400 MHz, CDCl3) δ 10.74 (s, 1H), 8.64 (dd, J1 = 1.00 Hz, J2 = 4.40 Hz, 1H), 8.40 (d, J = 7.20 Hz, 1H), 8.12–8.02 (m, 3H), 7.73 (s, 1H), 7.61–7.59 (m, 2H), 7.35 (dd, J1 = 4.53 Hz, J2 = 8.08 Hz, 1H), 7.23 (s, 1H), 5.02–5.00 (m, 2H), 1.25–1.09 (m, 12 H); 13C NMR (100 MHz, CDCl3) δ 161.2, 156.0, 146.6, 146.3, 144.5, 135.0, 132.7, 130.7, 126.9, 126.7, 126.5, 125.9, 123.7, 120.7, 120.0, 118.3, 70.9, 70.0, 22.0; HRMS (ESI+) m/z [M + H]+ calcd for C24H26BrN4O5: 529.1081, Found: 529.1077.
3fa. yellow solid (40.2 mg, 83%), Rf = 0.32 (25% EtOAc in hexane), mp 218.0–219.5 °C; 1H NMR (400 MHz, CDCl3) δ 10.40 (s, 1H), 8.33 (d, J = 7.70 Hz, 1H), 8.28 (d, J = 7.48 Hz, 1H), 8.06 (d, J = 8.52 Hz, 1H), 7.91 (t, J = 7.76 Hz, 1H), 7,76 (s, 1H), 7.65–7.55 (m, 3H), 7.24 (s, 1H), 5.02–4.99 (m, 2H), 1.26–1.10 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 160.9, 156.1, 150.3, 150.1, 140.4, 135.4, 132.3, 130.7, 127.5, 127.1, 126.8, 126.7, 125.8, 123.7, 121.3, 120.8, 118.8, 70.9, 70.0, 22.0; HRMS (ESI+) m/z [M + H]+ calcd for C24H26ClN4O5: 485.1586, Found: 485.1582.
3ga. yellow solid (44.7 mg, 95%), Rf = 0.32 (25% EtOAc in hexane), mp 195.5–197.0 °C; 1H NMR (400 MHz, CDCl3) δ 10.28 (s, 1H), 8.35 (d, J = 7.92 Hz, 1H), 8.25 (dd, J1 = 1.48 Hz, J2 = 7.36 Hz, 1H), 8.07–8.01 (m, 3H), 7.75 (s, 1H), 7.64–7.57 (m, 2H), 7.32 (s, 1H), 7.19 (dd, J1 = 1.96 Hz, J2 = 8.16 Hz, 1H), 5.02–4.99 (m, 2H), 1.25–1.10 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.0 (d, J = 243.57 Hz), 160.9, 156.1, 148.4 (d, J = 10.63 Hz), 143.0 (d, J = 10.63 Hz), 135.4, 132.2, 130.7, 127.0, 126.8, 126.7, 125.8, 123.8, 120.7, 120.3 (d, J = 3.66 Hz), 118.7, 113.2 (d, J = 35.47 Hz), 70.9, 70.0, 22.0; 19F NMR (376 MHz, CDCl3): δ -66.95 (s, 1F); HRMS (ESI+) m/z [M + H]+ calcd for C24H26FN4O5: 469.1882, Found: 469.1880.
3ha. pale yellow solid (43.1 mg, 89%), Rf = 0.32 (25% EtOAc in hexane), mp 170.6–172.4 °C; 1H NMR (400 MHz, CDCl3) δ 10.67 (s, 1H), 8.59 (d, J = 5.24 Hz, 1H), 8.38 (d, J = 7.89 Hz, 1H), 8.35 (d, J = 1.80 Hz, 1H), 8.09–8.04 (m, 2H), 7.75 (s, 1H), 7.62–7.56 (m, 2H), 7.52 (dd, J1 = 1.92 Hz, J2 = 5.20 Hz, 1H), 7.35 (s, 1H), 5.02–5.01 (m, 2H), 1.25–1.10 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 161.0, 156.1, 151.3, 149.0, 146.4, 135.2, 132.3, 130.7, 126.8, 126.6, 125.9, 123.8, 123.2, 120.6, 118.3, 70.9, 70.0, 22.0, 21.9; HRMS (ESI+) m/z [M + H]+ calcd for C24H26ClN4O5: 485.1586, Found: 485.1583.
3ia. pale yellow solid (45.0 mg, 97%), Rf = 0.32 (25% EtOAc in hexane), mp 192.1–194.0 °C; 1H NMR (400 MHz, CDCl3) δ 11.05 (s, 1H), 8.54 (d, J = 3.81 Hz, 1H), 8.37 (d, J = 7.24 Hz, 1H), 8.11–8.08 (m, 2H), 7.73 (s, 1H), 7.67 (d, J = 7.64 Hz, 1H), 7.61–7.55 (m, 2H), 7.40 (q, J = 7.74 Hz, 1H), 7.23 (s, 1H), 5.02–5.00 (m, 2H), 2.85 (s, 3H), 1.25–1.09 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 163.7, 156.0, 146.7, 145.5, 141.4, 136.4, 134.6, 133.1, 130.7, 127.1, 126.6, 126.3, 126.2, 126.0, 123.6., 121.0, 118.0, 70.8, 69.9, 22.0, 20.8; HRMS (ESI+) m/z [M + K]+ calcd for C25H28N4O5K: 503.1691, Found: 503.1691.
3ga. yellow solid (32.6 mg, 70%), Rf = 0.32 (25% EtOAc in hexane), mp 202.5–204.4 °C; 1H NMR (400 MHz, CDCl3) δ 10.89 (s, 1H), 8.42 (d, J = 7.57 Hz, 1H), 8.17–8.08 (m, 3H), 7.83–7.73 (m, 2H), 7.64–7.56 (m, 2H), 7.37 (d, J = 7.68 Hz, 1H), 7.26 (s, 1H), 5.02–4.99 (m, 2H), 2.70 (s, 3H), 1.37–1.00 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.4, 157.2, 156.1, 149.1, 137.9, 134.8, 132.8, 130.8, 126.9, 126.7, 126.4, 126.4, 126.0, 123.7, 120.8, 119.6, 118.1, 70.8, 70.0, 24.4, 22.0; HRMS (ESI+) m/z [M + K]+ calcd for C25H28N4O5K: 503.1691, Found: 503.1690.
3ka. yellow solid (32.3 mg, 67%), Rf = 0.32 (25% EtOAc in hexane), mp 191.0–192.5 °C; 1H NMR (400 MHz, CDCl3) δ 10.57 (s, 1H), 8.68 (d, J = 4.20 Hz, 1H), 8.36 (d, J = 7.80 Hz, 1H), 8.28 (d, J = 8.00 Hz, 1H), 8.05 (s, 1H), 7.94 (dt, J1 = 1.55 Hz, J2 = 9.26 Hz, 1H), 7.57–7.51 (m, 2H), 7.33 (d, J = 2.88 Hz, 1H), 7.26–7.23 (m, 2H), 5.02–4.99 (m, 2H), 3.96 (s, 3H), 1.29–1.09 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.3, 158.2, 156.0, 149.9, 148.2, 137.8, 135.3, 131.5, 128.6, 126.6, 126.2, 125.7, 123.2, 122.6, 119.6, 118.6, 100.4, 70.8, 69.9, 55.3, 22.0, 21.8; HRMS (ESI+) m/z [M + H]+ calcd for C25H29N4O6: 481.2082, Found: 481.2081.
3la. yellow solid (37.5 mg, 80%), Rf = 0.32 (25% EtOAc in hexane), mp 175.9–177.6 °C; 1H NMR (400 MHz, CDCl3) δ 9.90 (s, 1H), 8.70 (d, J = 4.20 Hz, 1H), 8.33 (d, J = 7.80 Hz, 1H), 7.97–7.92 (m, 3H), 7.68 (s, 1H), 7.55–7.52 (m, 1H), 7.49–7.46 (m, 2H), 7.20 (s, 1H), 5.02–4.99 (m, 2H), 2.46 (s, 3H), 1.37–1.12 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.9, 155.9, 149.6, 148.3, 137.6, 137.2, 133.2, 131.3, 130.3, 129.3, 128.6, 126.7, 126.6, 126.0, 123.0, 122.7, 70.9, 70.0, 22.0, 18.9; HRMS (ESI+) m/z [M + K]+ calcd for C25H28N4O5K: 503.1691, Found: 503.1690.
3ma. yellow solid (47.5 mg, 88%), Rf = 0.32 (25% EtOAc in hexane), mp 113.6–115.0 °C; 1H NMR (400 MHz, CDCl3) δ 13.96 (s, 1H), 9.14 (d, J = 8.50 Hz, 1H), 8.73 (d, J = 4.17 Hz, 1H), 8.38 (d, J = 7.84 Hz, 1H), 7.95–7.72 (m, 3H), 7.54–7.47 (m, 2H), 7.41 (d, J = 7.33 Hz, 1H), 7.20 (s, 1H), 5.02–4.99 (m, 2H), 4.25 (s, 2H), 3.84 (s, 2H), 3.19–2.98 (m, 4H), 1.25–1.03 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 163.4, 156.0, 151.0, 149.5, 147.9, 137.6, 135.9, 134.0, 133.0, 126.5, 126.4, 123.5, 120.4, 120.3, 117.3, 116.5, 70.8, 70.0, 65.5, 55.1, 54.3, 53.8, 22.0; HRMS (ESI+) m/z [M + K]+ calcd for C28H33N5O6K: 574.2062, Found: 574.2059.
3na. yellow solid (26.7 mg, 50%), Rf = 0.32 (25% EtOAc in hexane), mp 221.6–223.5 °C; 1H NMR (400 MHz, CDCl3) δ 9.65 (s, 1H), 8.30 (d, J = 7.88 Hz, 1H), 8.16–8.07 (m, 3H), 7.80–7.73 (m, 2H), 7.56–7.52 (m, 1H), 7.42–7.28 (m, 5H), 7.19 (s, 2H), 7.01 (t, J = 7.43 Hz, 1H), 5.04–5.02 (m, 2H), 1.34–1.08 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 161.9, 155.9, 149.5, 147.3, 142.4, 138.1, 137.0, 135.7, 433.4, 132.1, 130.9, 129.2, 128.1, 126.9, 125.8, 125.7, 125.4, 123.1, 121.8, 70.9, 70.0, 29.7, 22.0; HRMS (ESI+) m/z [M + K]+ calcd for C30H30N4O5K: 565.1848, Found: 565.1847.
3oa. yellow solid (41.0 mg, 80%), Rf = 0.32 (25% EtOAc in hexane), mp 181.1–183.9 °C; 1H NMR (400 MHz, CDCl3) δ 10.67 (s, 1H), 8.65–8.64 (m, 1H), 8.36 (d, J = 7.81 Hz, 1H), 8.12 (d, J = 7.33 Hz, 1H), 7.94–7.90 (m, 2H), 7.75 (s, 1H), 7.51–7.48 (m, 1H), 7.39 (t, J = 7.10 Hz, 1H), 7.30 (d, J = 6.88 Hz, 1H), 5.01–4.99 (m, 2H), 2.99 (s, 3H), 1.25–1.03 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.2, 156.0, 149.9, 148.2, 137.7, 136.4, 133.7, 133.1, 132.4, 130.5, 128.6, 126.5, 126.3, 125.6, 122.7, 121.9, 70.8, 69.9, 25.1, 22.0; HRMS (ESI+) m/z [M + K]+ calcd for C25H28N4O5K: 503.1691, Found: 503.1688.
3pa. yellow solid (34.1 mg, 68%), Rf = 0.32 (25% EtOAc in hexane), mp 185.4–187.0 °C; 1H NMR (400 MHz, CDCl3) δ 11.02 (s, 1H), 8.47–8.37 (m, 3H), 8.26 (d, J = 8.47 Hz, 1H), 8.19 (d, J = 8.33 Hz, 1H), 8.11 (s, 1H), 7.92 (d, J = 8.14 Hz, 1H), 7.85–7.79 (m, 2H), 7.68–7.59 (m, 3H), 7.29 (s, 1H), 5.04–5.02 (m, 2H), 1.27–1.11 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 162.4, 156.1, 149.6, 146.3, 138.0, 135.0, 132.8, 130.8, 130.4, 129.8, 129.5, 128.3, 127.8, 127.0, 126.7, 126.5, 126.0, 123.8, 120.8, 118.8, 118.2, 70.9, 70.0, 22.0; HRMS (ESI+) m/z [M + K]+ calcd for C28H28N4O5K: 539.1691, Found: 539.1690.
3qa.yellow solid (34.4 mg, 68%), Rf = 0.32 (25% EtOAc in hexane), mp 223.1–224.2 °C; 1H NMR (400 MHz, CDCl3) δ 11.16 (s, 1H), 9.78 (d, J = 7.92 Hz, 1H), 8.62 (d, J = 4.30 Hz, 1H), 8.44 (d, J = 7.26 Hz, 1H), 8.16–8.07 (m, 2H), 7.90 (d, J = 6.08 Hz, 2H), 7.77–7.71 (m, 3H), 7.63–7.57 (m, 2H), 7.20 (s, 1H), 5.02 (s, 1H), 1.26–1.06 (m, 12H); 13C NMR (100 MHz, CDCl3) δ 163.8, 156.1, 147.3, 140.0, 137.7, 134.9, 133.1, 130.8, 130.7, 129.0, 127.8, 127.4, 127.2, 126.9, 126.7, 126.4, 126.0, 125.1, 123.6, 121.0, 118.3, 70.9, 70.0, 22.0, 21.9; HRMS (ESI+) m/z [M + K]+ calcd for C28H28N4O5K: 539.1691, Found: 539.1692.
3ab. pale yellow solid (29.8 mg, 73%), Rf = 0.32 (25% EtOAc in hexane), mp 81.2–83.9 °C; 1H NMR (400 MHz, CDCl3) δ 10.81 (s, 1H), 8.69–8.68 (m, 1H), 8.40 (d, J = 7.94 Hz, 1H), 8.34 (d, J = 7.81 Hz, 1H), 8.10–8.08 (m, 2H), 7.90 (dt, J1 = 1.24 Hz, J2 = 7.68 Hz, 1H), 7.78 (s, 1H), 7.58 (t, J = 6.99 Hz, 2H), 7.52–7.49 (m, 2H), 7.29–7.20 (m, 2H), 7.05 (s, 1H), 5.15 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 162.3, 156.1, 149.7, 148.1, 137.8, 135.7, 135.4, 134.4, 133.0, 130.6, 128.5, 128.2, 128.0, 127.6, 127.0, 126.8, 126.7, 126.6, 126.1, 123.6, 120.8, 118.0, 68.4, 67.8; HRMS (ESI+) m/z [M + H]+ calcd for C32H27N4O5: 547.1976, Found: 547.1973.
3cb. yellow solid (48.4 mg, 83%), Rf = 0.32 (25% EtOAc in hexane), mp 68.9–70.2 °C; 1H NMR (400 MHz, CDCl3) δ 10.55 (s, 1H), 8.61 (d, J = 2.12 Hz, 1H), 8.33 (d, J = 7.89 Hz, 1H), 8.26 (d, J = 8.33 Hz, 1H), 8.09–8.01 (m, 2H), 7.81–7.79 (m, 3H), 7.59–7.50 (m, 2H), 7.30–7.91 (m, 9H), 7.04 (s, 1H), 5.14 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 161.5, 156.2, 147.8, 147.2, 137.5, 135.7, 135.6, 135.5, 134.7, 132.7, 130.7, 128.5, 128.3, 128.2, 127.6, 127.0, 126.8, 126.7, 126.0, 123.8, 123.6, 120.7, 118.3, 68.4, 67.8; HRMS (ESI+) m/z [M + H]+ calcd for C32H26ClN4O5: 581.1586, Found: 581.1584.
3bd. pale yellow solid (58.6 mg, 94%), Rf = 0.32 (25% EtOAc in hexane), mp 69.4–71.6 °C; 1H NMR (400 MHz, CDCl3) δ 10.55 (s, 1H), 8.71 (d, J = 1.92 Hz, 1H), 8.32 (d, J = 7.93 Hz, 1H), 8.19–8.10 (m, 2H), 8.01 (d, J = 8.61 Hz, 1H), 7.94 (d, J = 7.72 Hz, 1H), 7.83–7.75 (m, 2H), 7.58–7.49 (m, 2H), 7.26–7.18 (m, 9H), 7.03 (s, 1H), 5.13 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 161.6, 156.2, 149.4, 148.2, 140.5, 135.7, 135.5, 134.8, 132.6, 130.7, 128.5, 128.3, 128.2, 128.1, 127.6, 127.0, 126.8, 126.7, 126.0, 124.6, 124.0, 123.8, 120.6, 118.3, 68.4, 67.8; HRMS (ESI+) m/z [M + H]+ calcd for C32H26BrN4O5: 625.1081 Found: 625.1080.
3eb. white solid (41.8 mg, 67%), Rf = 0.32 (25% EtOAc in hexane), mp 74.1–75.3 °C; 1H NMR (400 MHz, CDCl3) δ 10.74 (s, 1H), 8.63 (d, J = 4.05 Hz, 1H), 8.38 (d, J = 7.87 Hz, 1H), 8.10–8.01 (m, 3H), 7.76 (s, 1H), 7.58–7.50 (m, 3H), 7.34–7.72 (m, 10H), 7.05 (s, 1H), 5.15 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 161.1, 156.1, 146.5, 146.2, 144.5, 135.6, 135.4, 134.4, 132.9, 130.5, 128.5, 128.3, 128.1, 127.6, 126.9, 136.9, 126.6, 126.0, 123.5, 120.7, 120.0, 118.1, 68.4, 67.9; HRMS (ESI+) m/z [M + H]+ calcd for C32H26BrN4O5: 625.1081 Found: 625.1080.
3fb. pale yellow solid (41.9 mg, 72%), Rf = 0.32 (25% EtOAc in hexane), mp 75.9–77.3 °C; 1H NMR (400 MHz, CDCl3) δ 10.37 (s, 1H), 8.29–8.23 (m, 2H), 8.03 (d, J = 8.56 Hz, 2H), 7.84–7.70 (m, 3H), 7.60 (t, J = 7.05 Hz, 1H), 7.51 (d, J = 7.88 Hz, 2H), 7.28–7.20 (m, 9H), 7.04 (s, 1H), 5.14 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 161.0, 156.2, 150.2, 150.1, 140.4, 135.6, 135.4, 135.0, 132.5, 130.6, 128.5, 128.3, 128.2, 127.6, 127.5, 127.1, 126.8, 126.0, 123.7, 121.3, 120.8, 118.7, 68.4, 67.8; HRMS (ESI+) m/z [M + H]+ calcd for C32H26ClN4O5: 581.1586, Found: 581.1585.
3hb. pale yellow solid (46.7 mg, 80%), Rf = 0.32 (25% EtOAc in hexane), mp 70.5–71.1 °C; 1H NMR (400 MHz, CDCl3) δ 10.65 (s, 1H), 8.57 (d, J = 5.24 Hz, 1H), 8.36–8.33 (m, 2H), 8.03 (d, J = 8.66 Hz, 2H), 7.77 (s, 1H), 7.59–7.55 (m, 2H), 7.50 (dd, J1 = 1.96 Hz, J2 = 5.16 Hz, 2H), 7.30–7.20 (m, 9H), 7.04 (s, 1H), 5.14 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 161.1, 156.1, 151.2, 149.0, 146.4, 135.6, 135.4, 134.7, 132.7, 130.6, 128.5, 128.3, 128.2, 127.7, 127.0, 126.9, 126.7, 126.1, 123.6, 123.2, 120.7, 118.1, 68.5, 67.9; HRMS (ESI+) m/z [M + H]+ calcd for C32H26ClN4O5: 581.1586, Found: 581.1586.
3ib. white solid (44.7 mg, 80%), Rf = 0.32 (25% EtOAc in hexane), mp 67.1–69.5 °C; 1H NMR (400 MHz, CDCl3) δ 11.05 (s, 1H), 8.52 (d, J = 3.61 Hz, 1H), 8.35 (d, J = 7.92 Hz, 1H), 8.07 (d, J = 8.73 Hz, 2H), 7.75 (s, 1H), 7.65–7.49 (m, 4H), 7.38 (dd, J1 = 4.46 Hz, J2 = 7.72 Hz, 2H), 7.28–7.20 (m, 8H), 7.05 (s, 1H), 5.14 (s, 4H), 2.82 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 163.8, 156.1, 146.7, 145.5, 141.4, 136.4, 135.7, 135.5, 134.1, 133.5, 130.6, 128.5, 128.3, 128.2, 127.6, 127.1, 126.9, 126.5, 126.2, 123.5, 121.1, 117.8, 68.4, 67.8, 20.8; HRMS (ESI+) m/z [M + K]+ calcd for C33H28N4O5K: 599.1691, Found: 599.1692.
3ac. pale yellow solid (45.8 mg, 95%), Rf = 0.32 (25% EtOAc in hexane), mp 215.5–216.8 °C; 1H NMR (400 MHz, CDCl3) δ 10.80 (s, 1H), 8.69 (d, J = 4.28 Hz, 1H), 8.43 (d, J = 7.29 Hz, 1H), 8.34 (d, J = 7.77 Hz, 1H), 8.10–8.08 (m, 2H), 7.92 (t, J = 7.26 Hz, 1H), 7.73 (s, 1H), 7.59–7.57 (m, 2H), 7.51 (t, J = 6.04 Hz, 1H), 7.11 (s, 1H), 1.48–1.25 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 162.2, 155.5, 149.9, 148.1, 137.8, 135.6, 132.4, 130.7, 126.6, 126.3, 123.9, 122.5, 120.7, 118.0, 82.0, 81.3, 28.2, 28.0; HRMS (ESI+) m/z [M + H]+ calcd for C26H31N4O5: 479.2289, Found: 479.2288.
3cc. white solid (25.8 mg, 50%), Rf = 0.32 (25% EtOAc in hexane), mp 170.1–172.2 °C; 1H NMR (400 MHz, CDCl3) δ 10.56 (s, 1H), 8.65 (d, J = 2.12 Hz, 1H), 8.38 (d, J = 7.54 Hz, 1H), 8.31 (d, J = 8.32 Hz, 1H), 8.06–8.04 (m, 2H), 7.92 (dd, J1 = 2.17 Hz, J2 = 8.33 Hz, 1H), 7.22 (s, 1H), 7.62–7.57 (m, 2H), 7.00 (s, 1H), 1.49–1.30 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 161.3, 155.4, 148.0, 147.2, 137.5, 135.7, 135.5, 132.0, 130.7, 126.7, 126.6, 126.4, 125.9, 125.5, 123.9, 123.6, 120.6, 118.2, 82.1, 81.4, 29.6, 28.2, 28.0; HRMS (ESI+) m/z [M + H]+ calcd for C26H30ClN4O5: 513.1899, Found: 513.1901.
3dc. pale yellow solid (29.4 mg, 53%), Rf = 0.32 (25% EtOAc in hexane), mp 182.7–184.9 °C; 1H NMR (400 MHz, CDCl3) δ 10.57 (s, 1H), 8.77 (d, J = 1.95 Hz, 1H), 8.38 (d, J = 7.58 Hz, 1H), 8.24 (d, J = 8.41 Hz, 1H), 8.09–8.04 (m, 3H), 7.73 (s, 1H), 7.62–7.57 (m, 2H), 6.99 (s, 1H), 1.55–1.30 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 161.5, 154.8, 149.4, 148.4, 140.5, 135.7, 132.0, 130.7, 126.7, 126.4, 125.4, 124.5, 123.9, 120.6, 118.2, 82.1, 81.4, 29.6, 28.2, 28.0; HRMS (ESI+) m/z [M + H]+ calcd for C26H30BrN4O5: 557.1394, Found: 557.1395.
3fc. pale yellow solid (34.8 mg, 68%), Rf = 0.32 (25% EtOAc in hexane), mp 207.8–209.6 °C; 1H NMR (400 MHz, CDCl3) δ 10.39 (s, 1H), 8.33 (d, J = 7.78 Hz, 1H), 8.27 (d, J = 7.35 Hz, 1H), 8.05 (d, J = 8.80 Hz, 2H), 7.90 (t, J = 7.79 Hz, 1H), 7.73 (s, 1H), 7.64–7.57 (m, 2H), 7.55 (d, J = 7.78 Hz, 1H), 7.05 (s, 1H), 1.48–1.25 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 160.9, 155.5, 154.7, 150.4, 150.1, 140.4, 136.0, 131.9, 130.7, 127.4, 127.0, 126.6, 125.3, 123.9, 121.2, 120.7, 118.8, 82.1, 82.5, 28.2, 28.0; HRMS (ESI+) m/z [M + Na]+ calcd for C26H29ClN4O5Na: 535.1719, Found: 535.1724.
3ic. yellow solid (39.5 mg, 80%), Rf = 0.32 (25% EtOAc in hexane), mp 197.0–198.1 °C; 1H NMR (400 MHz, CDCl3) δ 11.04 (s, 1H), 8.54–8.53 (m, 1H), 8.37 (d, J = 7.09 Hz, 1H), 8.10–8.07 (m, 2H), 7.70–7.65 (m, 2H), 7.59–7.55 (m, 2H), 7.40 (dd, J1 = 4.58 Hz, J2 = 7.70 Hz, 1H), 7.03 (s, 1H), 2.85 (s, 3H), 1.48–1.25 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 163.7, 155.4, 146.8, 145.5, 141.4, 136.3, 135.2, 132.8,130.7, 127.0, 126.4, 126.2, 126.2, 123.7, 121.0, 118.0, 82.0, 81.3, 28.2, 28.0, 20.8; HRMS (ESI+) m/z [M + H]+ calcd for C27H33N4O5: 493.2445, Found: 493.2446.
3jc. yellow solid (38.7 mg, 78%), Rf = 0.32 (25% EtOAc in hexane), mp 201.3–203.8 °C; 1H NMR (400 MHz, CDCl3) δ 10.83 (s, 1H), 8.41 (d, J = 7.48 Hz, 1H), 8.15 (d, J = 7.62 Hz, 1H), 8.09–8.07 (m, 2H), 7.81 (t, J = 7.68 Hz, 1H), 7.73 (s, 1H), 7.37 (d, J = 7.65 Hz, 1H), 7.06 (s, 1H), 2.70 (s, 3H), 1.48–1.30 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 162.4, 157.2, 155.4, 149.1, 137.9, 132.5, 130.8, 126.9, 126.4, 126.3, 123.9, 120.7, 119.6, 118.1, 82.0, 81.4, 28.2, 28.0, 24.4; HRMS (ESI+) m/z [M + H]+ calcd for C27H32N4O5: 493.2445, Found: 493.2448.
3nc. yellow solid (20.9 mg, 38%), Rf = 0.32 (25% EtOAc in hexane), mp 201.5–203.3 °C; 1H NMR (400 MHz, CDCl3) δ 9.62 (s, 1H), 8.29 (d, J = 6.17 Hz, 1H), 8.16 (d, J = 3.91 Hz, 1H), 8.07 (d, J = 7.73 Hz, 2H), 7.77–7.73 (m, 2H), 7.54 (t, J = 7.21 Hz, 1H), 3.39–3.26 (m, 4H), 7.19 (s, 1H), 7.02–6.98 (m, 2H), 1.56–1.34 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 161.9, 154.9, 149.6, 147.3, 142.4, 138.0, 137.0, 136.2, 133.0, 132.1, 130.8, 129.1, 128.1, 126.8, 125.7, 125.5, 123.2, 121.8, 82.1, 81.4, 29.6, 28.2, 28.1; HRMS (ESI+) m/z [M + H]+ calcd for C32H35N4O5: 555.2602, Found: 555.2603.
3oc. yellow solid (40.8 mg, 83%), Rf = 0.32 (25% EtOAc in hexane), mp 202.5–204.7 °C; 1H NMR (400 MHz, CDCl3) δ 10.65 (s, 1H), 8.65 (d, J = 4.43 Hz, 1H), 8.35 (d, J = 7.82 Hz, 1H), 7.94–7.88 (m, 2H), 7.33–7.32 (m, 1H), 7.51–7.48 (m, 1H), 7.39 (t, J = 7.15 Hz, 1H), 7.29 (d, J = 6.91 Hz, 1H), 7.03 (s, 1H), 2.99 (s, 3H), 1.47–1.43 (m, 18H); 13C NMR (100 MHz, CDCl3) δ 162.2, 155.3, 154.9, 149.9, 148.1, 137.7, 137.0, 133.3, 133.0, 132.3, 130.3, 128.5, 126.5, 126.1, 125.2, 122.1, 82.0, 81.3, 28.2, 28.0, 25.1; HRMS (ESI+) m/z [M + H]+ calcd for C27H33N4O5: 493.2445, Found: 493.2443.

4. Conclusions

In summary, we developed a simple and efficient protocol for silver(I)-catalyzed amination of 1-naphthylamine derivatives with azodicarboxylate at the C4 site in acetone at room temperature, leading to the target products in mostly good yields. Note that this reaction might proceed with a self-redox process under external-oxidant and additive-free conditions. The reaction is compatible with a variety of functional groups on both the pyridine and naphthene rings of 1-naphthylamine derivatives.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/catal12091006/s1, Table S1: Optimization of Catalyst and Solvent, Table S2: Optimization of Catalyst Loading, Table S3: Optimization of Time.

Author Contributions

F.Y., Y.W. review and editing, and supervision. Y.Z., M.P. the main part of the experimental and data collection, writing—original draft preparation. All authors have read and agreed to the published version of the manuscript.

Funding

We are grateful to the National Natural Science Foundation of China (nos. 21172200, 21102134) for its financial support.

Data Availability Statement

The Supporting Information is available free of charge on the website. Experimental details.

Acknowledgments

The authors would like to thank Zhen Liu from East China University of Science and Technology for support in mechanistic calculation.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 12 01006 sch001 550
Scheme 1. The C4-H Amination of 1-Naphthylamines. (a) C4-H Amination of 1-Naphthylamines under basic or acidic conditions (b) C4-H Amination of 1-Naphthylamines under basic and acidic-free conditions.
Scheme 1. The C4-H Amination of 1-Naphthylamines. (a) C4-H Amination of 1-Naphthylamines under basic or acidic conditions (b) C4-H Amination of 1-Naphthylamines under basic and acidic-free conditions.
Catalysts 12 01006 sch001
Catalysts 12 01006 sch002 550
Scheme 2. Substrate Scope of 1-Naphthylamine Derivatives with Diisopropyl Azodicarboxylate (2a).
Scheme 2. Substrate Scope of 1-Naphthylamine Derivatives with Diisopropyl Azodicarboxylate (2a).
Catalysts 12 01006 sch002
Catalysts 12 01006 sch003 550
Scheme 3. Substrate Scope of 1-Naphthylamine Derivatives with Dibenzyl Azodicarboxylate (2b) or Di-tert-butyl Azodicarboxylate (2c).
Scheme 3. Substrate Scope of 1-Naphthylamine Derivatives with Dibenzyl Azodicarboxylate (2b) or Di-tert-butyl Azodicarboxylate (2c).
Catalysts 12 01006 sch003
Catalysts 12 01006 sch004 550
Scheme 4. Synthetic Application. (a) Gram-Scale Experiment for the amination of 1a. (b) Further alkylation and arylation of Products 3.
Scheme 4. Synthetic Application. (a) Gram-Scale Experiment for the amination of 1a. (b) Further alkylation and arylation of Products 3.
Catalysts 12 01006 sch004
Catalysts 12 01006 sch005 550
Scheme 5. Mechanistic Study. (a) Some Substrates Analogues. (b) Effect of Radical Inhibitors on the Reaction.
Scheme 5. Mechanistic Study. (a) Some Substrates Analogues. (b) Effect of Radical Inhibitors on the Reaction.
Catalysts 12 01006 sch005
Catalysts 12 01006 sch006 550
Scheme 6. Possible Pathway.
Scheme 6. Possible Pathway.
Catalysts 12 01006 sch006
Catalysts 12 01006 g001 550
Figure 1. The intermediate B was optimized using B3LYP in combination with the LANL2TZ effective core potential (ECP) for Ag, and 6–311G (d, p) for all other atoms. The D3 version of Grimme’s dispersion (GD3) and Truhlar’s SMD solvation model with acetone as the model solvent was adopted for the geometry optimization. Spin densities (red) are in atomic units. The single occupied molecular orbital (SOMO) is depicted with 0.03 au−3/2 isovalue.
Figure 1. The intermediate B was optimized using B3LYP in combination with the LANL2TZ effective core potential (ECP) for Ag, and 6–311G (d, p) for all other atoms. The D3 version of Grimme’s dispersion (GD3) and Truhlar’s SMD solvation model with acetone as the model solvent was adopted for the geometry optimization. Spin densities (red) are in atomic units. The single occupied molecular orbital (SOMO) is depicted with 0.03 au−3/2 isovalue.
Catalysts 12 01006 g001
Table
Table 1. Optimization of the reaction conditions a.
Table 1. Optimization of the reaction conditions a.
Catalysts 12 01006 i001
EntryCatalystSolventYield (%) b
1Ag2ODCE80
2Ag2Odioxane90
3Ag2Oacetone97
4Ag2OTHF90
5Ag2ODME80
6Ag2ODCM<5
7CuOacetone<5
8Cu2Oacetone<5
9Fe2O3acetone<5
10AgOAcacetone<5
11-acetone<5
12 cAg2Oacetone88
13 dAg2Oacetone46
a Reaction conditions: 1a (0.1 mmol), 2a (0.2 mmol), catalyst (10 mol%) in solvent (1 mL) at room temperature for 8 h. b Isolated yield based on 1a. c For 7 h. d With a catalyst loading of 5 mol%.
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Zhang, Y.; Pei, M.; Yang, F.; Wu, Y. Silver(I)-Catalyzed C4-H Amination of 1-Naphthylamine Derivatives with Azodicarboxylates at Room Temperature. Catalysts 2022, 12, 1006. https://doi.org/10.3390/catal12091006

AMA Style

Zhang Y, Pei M, Yang F, Wu Y. Silver(I)-Catalyzed C4-H Amination of 1-Naphthylamine Derivatives with Azodicarboxylates at Room Temperature. Catalysts. 2022; 12(9):1006. https://doi.org/10.3390/catal12091006

Chicago/Turabian Style

Zhang, Yuxue, Mengxue Pei, Fan Yang, and Yangjie Wu. 2022. "Silver(I)-Catalyzed C4-H Amination of 1-Naphthylamine Derivatives with Azodicarboxylates at Room Temperature" Catalysts 12, no. 9: 1006. https://doi.org/10.3390/catal12091006

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