Copper-Catalyzed C5–H Sulfenylation of Unprotected 8

By acting as directing group (DG), the 8-aminoquinoline has shown marvellous function in assisting the activation of numerous C(sp)-H, C(sp2)-H, C(sp3...
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Cite This: J. Org. Chem. 2018, 83, 11385−11391

Copper-Catalyzed C5−H Sulfenylation of Unprotected 8‑Aminoquinolines Using Sulfonyl Hydrazides Qing Yu, Yiming Yang, Jie-Ping Wan, and Yunyun Liu* College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P.R. China

J. Org. Chem. 2018.83:11385-11391. Downloaded from pubs.acs.org by TULANE UNIV on 01/13/19. For personal use only.

S Supporting Information *

ABSTRACT: The synthesis of C5-sulfenylated 8-aminoquinolines using unprotected 8-aminoquinolines and sulfonyl hydrazides is achieved via the catalysis of CuI. The reactions are hypothesized to proceed via the Cu(I)− Cu(II)−Cu(I) catalytic processes induced by aerobic oxidation and singleelectron transfer on the Cu(II)−8-aminoquinoline complex. This work discloses an unprecedented step-efficient method for the synthesis of C5sulfenylated 8-aminoquinolines bearing a useful free NH2 group.

B

aminoquinolines is inarguably a powerful tool in the synthesis of C5-substituted 8-aminoquinoline libraries of enriched diversity. However, one common and mandatory precondition in all of these known reactions is that the amino group must be first acylated so that the expected C−H bond transformation can smoothly take place (Scheme 1A). Such operation is thus a

y acting as the directing group (DG), the 8-aminoquinoline has shown marvelous function in assisting the activation of numerous C(sp)−H, C(sp2)−H, and C(sp3)−H bonds in amides via transition metal catalysis.1 Notably, alongside the impressive application as DG in C−H activation, the 8-aminoquline itself has been identified as a useful aromatic C−H bond donor in the remote activation of the C5 position when the amino group is acylated. Because of the inherent privilege of the 8-aminoquiline as a main fragment in many natural products and lead compounds (Figure 1),2 the remote

Scheme 1. C5−H Sulfenylation: N-Acyl 8-Aminoquinolines vs Unprotected 8-Aminoquinolines

Figure 1. Some 8-aminoquinoline-based natural products and lead compounds.

activation and functionalization of the quinoline C−H bond directed by the 8-amido group has rapidly gained splendid progress. During the past several years, a large number of catalytic and synthetic methods for the remote C−H transformation have been realized as reliable tools for the synthesis of diversified 8-aminoquinoline derivatives. For example, for the C−C bond construction, the C5−H perfluoroalkylation,3 alkylation,4 as well as allylation5 have been accomplished by different groups. On the other hand, the examples on the formation of a C5−heteroatom bond, as known in literature, cover the C−H halogenation,6 amination,7 nitration,8 azidation,9 acyloxylation,10 and etherification.11 Notably, as important advances, the remote 8-amidoquinoline C−H activation reactions enabling the formation of new C−S/ C−Se bonds, including chalcogenation,12 thio/selenocyanation,13 and sulfonylation,14 have also been realized. According to these results, the C5−H bond functionalization of 8© 2018 American Chemical Society

restriction for the synthesis of those useful N-unsubstituted or N-alkyl 8-aminoquinolines (see Figure 1) because of the low step economy associated with the additional experiments of the previous N-acylation as well as the later deprotection. In this context, a catalytic or synthetic method allowing the direct C5−H bond activation on the unprotected 8-aminoquinolines is thus authentically desirable. Sulfonyl hydrazides are bench-stable chemicals showing universal application in organic synthesis. In previous works, sulfonyl hydrazides have been found as practical donors of various organic fragments such as sulfonyl, sulfenyl, aryl, hydrazide, and carbene precursor.15 In addition to introducing Received: July 2, 2018 Published: August 6, 2018 11385

DOI: 10.1021/acs.joc.8b01658 J. Org. Chem. 2018, 83, 11385−11391

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The Journal of Organic Chemistry

of the quick evaporation of the solvent at the reflux temperature (entries 16−18, Table 1). Finally, heightening and lowering the reaction temperature resulted in 3a with lower yield (entries 19 and 20, Table 1). In order to explore the synthetic scope of this C−H sulfenylation reaction, a class of different aryl-functionalized sulfonyl hydrazides 2 were employed to react with unprotected 8-aminoquinolines 1. As shown in Table 2, the results

novel reaction pathways enabling sophisticated syntheses, another notable advantage of the sulfonyl hydrazides is their friendliness to operators as odorless alternatives of thiols.16 On the basis of our recent efforts in developing step-economical C−H activation and functionalization reactions,17 we report herein the first direct C5−H sulfenylation of unprotected 8aminoquinolines by employing sulfonyl hydrazides as the sulfenylating reagents (Scheme 1B). At the beginning, the reaction between 8-aminoquinoline 1a and tosyl hydrazide 2a was selected for initial investigation. By running this reaction in the presence of 15 mol % of CuI in pxylene, we acquired the C5-sufenylated product 3a with low yield (entry 1, Table 1). Employing Na2CO3 as a base additive

Table 2. Scope on the Free Amino and N-Alkyl 8Aminoquinoline C5-Sulfenylationa,b

Table 1. Optimization of the Conditions for the C5−H Sulfenylation of 8-Aminoquinolinea

entry

catalyst

solvent

base

temp (°C)

yield (%)b

1 2 3c 4d 5e 6f 7 8 9 10 11 12 13 14 15 16 17 18 19 20

CuI CuI CuI CuI CuI CuI CuBr CuBr2 Cu(OAc)2 CuCl2 CuO CuI CuI CuI CuI CuI CuI CuI CuI CuI

p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene p-xylene DMF DMSO toluene p-xylene p-xylene

Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 DBU Et3N NaHCO3 NaOAc Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3

120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 reflux 110 130

13 67 38 35 33 8 trace trace nr trace nr 20 32 nr nr nr nr 18 23 37

a

Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), CuI (0.03 mmol), Na2CO3 (0.6 mmol) in p-xylene (2.0 mL), stirred at 120 °C for 12 h under air atmosphere. bIsolated yield based on 1.

indicated that this sulfenylation protocol tolerated aryl sulfonyl hydrazides containing diverse functional groups, including those ones with different electron effects and locations. In the reaction using para-substituted phenyl sulfonyl hydrazides, the substrates containing an electron-withdrawing group usually afforded products with yields lower than those of equivalent reactions employing sulfonyl hydrazides containing electrondonating substituents (3a−3h, Table 1). On the other hand, phenyl sulfonyl hydrazides possessing ortho-substitution provided the products with yields lower than those of parasubstituted substrates (3a, 3e vs 3i, 3j, Table 2), indicating the presence of negative steric hindrance. For the reactions employing fused aryl-functionalized substrates, a similar negative effect of the electron-withdrawing group was also found (3k vs 3l, Table 2). In addition, when the 3-methyl 8aminoquinline was used to react with various aryl sulfonyl hydrazides, related products were also acquired with moderate to good yields (3m−3q, Table 2). Notably, the N-alkylated 8aminoquinolines could also take part in this C5-sulfenylation reaction, but the products were afforded with much lower yield (3r, 3s, Table 2), suggesting that the free NH2 group in the quinoline substrate was positive for this sulfenylation process. However, no such C−S bond-forming reaction was observed when methyl sulfonyl hydrazide was employed to react with 1a under the standard conditions. On the basis of 8-aminoquinoline’s reaction, an entry employing aniline and tosyl hydrazide

a

Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol), copper catalyst (0.03 mmol), base (0.6 mmol) in solvent (2.0 mL), stirred at 120 °C for 12 h under air atmosphere; nr = no expected reaction. bYield of isolated product based on 1a. cCuI (0.02 mmol). dCuI (0.04 mmol). e Na2CO3 (0.4 mmol). fNa2CO3 (0.8 mmol).

led to a dramatic improvement in the yield of 3a (entry 2, Table 1). Varying the amount of CuI as well as Na2CO3 provided the target product with inferior yield (entries 3−6, Table 1). Further screening on copper catalysts such as CuBr, CuBr2, Cu(OAc)2, CuCl2, and CuO showed that all of these copper species were not practical for the expected reaction (entries 7−11, Table 1). The parallel experiments using different base additives, including DBU, Et3N, NaHCO3, and NaOAc, proved that they were all not proper additives because lower yield or no expected product formation was observed (entries 12−15, Table 1). The subsequent work in running the reaction in different media suggested that no expected reaction took place in polar solvents such DMSO or DMF, and lower yield was obtained in the entry using toluene, possibly because 11386

DOI: 10.1021/acs.joc.8b01658 J. Org. Chem. 2018, 83, 11385−11391

Note

The Journal of Organic Chemistry

On the basis of the reaction outcome from the synthetic reactions and control experiments, a possible mechanism is proposed for the reaction (Scheme 4). First, the sulfonyl

was also conducted, but no expected sulfonylation reaction occurred. Notably, no other regioisomeric product was oberved in the above reactions, indicating the ideal regioselectivity of this C−H sulfenylation protocol. Because no protection was required in the synthesis of sulfenylated products 3, the presence of the free NH2 group in products provided a good platform for the synthesis of different N-substituted derivatives. For example, the N-acyl 5sulfenyl 8-aminoquinolines 5 can be easily accessed via the Et3N-promoted acylation by using products 3 and acyl chloride 4 (Scheme 2).

Scheme 4. Proposed Reaction Mechanism

Scheme 2. Synthesis of N-Acyl C5-Sulfenyl 8Aminoquinolines

hydrazide undergoes a featured reductive coupling to provide benzenesulfonothioate 6.16c,d Meanwhile, the aerobic heating enables the oxidation of Cu(I) to Cu(II), which can incorporate 8-aminoquinolines 1 to provide Cu(II) complex A with the assistance of a base as in the well-documented Cu(II)-catalyzed C5−H functionalization of 8-amidoquinolines.6−14 The presence of Cu(II) species then initiates a single-electron transfer (SET) on A to provide free radical intermediate B, and the Cu(I) is simultaneously regenerated. On the other hand, intermediate 6 gets further reduced to yield disulfide 7 in the presence of sulfonyl hydrazide.16d,e The arylthio free radical 8 resulting from the homocleavage of disulfide then quickly reacts with B to yield another Cu(II) complex C. Subsequently, C is further transformed into D via intramolecular proton transfer. Finally, products 3 are provided from D, and the Cu(II) is released for further catalytic cycle. In summary, by employing a CuI/base catalytic system, we accomplished the first C5−H sulfenylation reaction of unprotected 8-aminoquinolines, wherein sulfonyl hydrazides are employed as the sulfenylating reagents. The direct reaction of the free NH2-functionalized quinolines shows incomparable advantages by affording products containing the free NH2 group without requiring any additional operation of protection or deprotection. This present work offers a uniquely steeconomical platform to access 8-aminoquinoline derivatives with divergent N-substitution.

In order to gain information on reaction mechanism, related control experiments were carried out. We first examined the reaction of N-acylated 8-aminoquinoline 6 with tosyl hydrazide 2a under the standard conditions, but the expected C5sulfenylation on 6 did not occur, implying that the free NH2 group was crucial for the titled reaction (eq 1). In addition, the model reaction carried out in the presence of TEMPO and BHT showed that the formation of the target product was evidently inhibited, confirming that the free radical reaction pathway was involved (eqs 2 and 3, Scheme 3). Subsequently, the reaction employing 8-aminoquinoline 1a with stoichiometric CuI was peformed, but no reaction took place, suggesting against the presence of an iodinated intermediate (eq 4, Scheme 3). On the other hand, subjecting only tosyl hydrazide 2a to the standard conditions provided mixed benzenesulfonothioate 6a and disulfide 7a (eq 5, Scheme 3), suggesting that compounds of type 6 and 7 were possible intermediates. Based on the results from the above experiment, the benzenesulfonothioate 6a and disulfide 7a were than subjected to react with 8-aminoquinoline. As expected, both reactions provided product 3a (eqs 6 and 7, Scheme 3). Scheme 3. Control Experiments

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DOI: 10.1021/acs.joc.8b01658 J. Org. Chem. 2018, 83, 11385−11391

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The Journal of Organic Chemistry

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H), 6.91 (d, J = 7.8 Hz, 1 H), 6.82 (d, J = 8.6 Hz, 2 H), 5.35 (s, 2 H); 13 C NMR (100 MHz, CDCl3) δ 147.6, 146.4, 138.9, 137.8, 134.5, 131.8, 130.5, 127.5, 122.6, 118.5, 113.3, 109.4; ESI-HRMS calcd for C15H12BrN2S [M + H]+ 330.9899, found 330.9893. 5-((4-Nitrophenyl)thio)quinolin-8-amine (3g): Red solid; 33.0 mg, 55% yield; mp 87−88 °C; 1H NMR (400 MHz, CDCl3) δ 8.81− 8.78 (m, 1 H), 8.44 (d, J = 8.0 Hz, 1 H), 7.97 (d, J = 8.0 Hz, 2 H), 7.73 (d, J = 7.8 Hz, 1 H), 7.42 (dd, J = 8.0, 4.0 Hz, 1 H), 7.01−6.93 (m, 3H), 5.44 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 150.0, 147.8, 147.1, 145.0, 138.8, 138.3, 134.0, 130.5, 125.2, 124.0, 122.9, 110.8, 109.4; ESI-HRMS calcd for C15H12N3O2S [M + H]+ 298.0645, found 298.0650. 4-((8-Aminoquinolin-5-yl)thio)benzonitrile (3h): Red solid; 27.0 mg, 49% yield; mp 181−182 °C; 1H NMR (400 MHz, CDCl3) δ 8.79 (dd, J = 4.2, 1.6 Hz, 1 H), 8.46 (dd, J = 8.6, 1.6 Hz, 1 H), 7.73 (d, J = 7.8 Hz, 1 H), 7.43 (dd, J = 8.6, 4.2 Hz, 1 H), 7.39−7.36 (m, 2 H), 6.95 (t, J = 7.8 Hz, 3 H), 5.46 (s, 3 H); 13C NMR (100 MHz, DMSOd6) δ 149.1, 147.9, 147.6, 139.1, 138.5, 133.7, 133.1, 130.5, 125.8, 123.6, 119.3, 108.9, 107.4, 107.3; ESI-HRMS calcd for C16H12N3S [M + H]+ 278.0746, found 278.0748. 5-(o-Tolylthio)quinolin-8-amine (3i): Black solid; 28.0 mg, 53% yield; mp 85−86 °C; 1H NMR (400 MHz, CDCl3) δ 8.76 (dd, J = 4.0, 1.2 Hz, 1 H), 8.52 (dd, J = 8.6, 1.0 Hz, 1 H), 7.68 (d, J = 7.8 Hz, 1 H), 7.38 (dd, J = 8.4, 4.2 Hz, 1 H), 7.14 (d, J = 7.2 Hz, 1 H), 6.98− 6.92 (m, 2 H), 6.85 (t, J = 7.6 Hz, 1 H), 6.44 (d, J = 7.8 Hz, 1 H), 5.16 (s, 2 H), 2.48 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 147.5, 145.9, 138.9, 138.5, 137.5, 134.8, 130.7, 129.9, 126.3, 125.7, 124.7, 122.4, 109.7, 20.0; ESI-HRMS calcd for C16H15N2S [M + H]+ 267.0950, found 267.0952. 5-((2-Chlorophenyl)thio)quinolin-8-amine (3j): Black solid; 31.5 mg, 55% yield; mp 127−128 °C; 1H NMR (400 MHz, CDCl3) δ 8.77 (d, 1 H), 8.51 (dd, J = 8.4, 1.4 Hz, 1 H), 7.74 (d, J = 7.8 Hz, 1 H), 7.40 (dd, J = 8.4, 4.0 Hz, 1 H), 7.33 (dd, J = 7.8, 1.0 Hz, 1 H), 6.99− 6.93 (m, 2 H), 6.89−6.84 (m, 1 H), 6.35 (dd, J = 8.0, 1.4 Hz, 1 H), 5.35 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 147.6, 146.6, 138.9, 138.3, 134.6, 130.8, 130.2, 129.4, 127.0, 126.5, 125.5, 122.7, 112.3, 109.6; ESI-HRMS calcd for C15H12ClN2S [M + H]+ 287.0404, found 287.0408. 5-(Naphthalen-2-ylthio)quinolin-8-amine (3k): Black liquid; 39.0 mg, 64% yield; 1H NMR (400 MHz, CDCl3) δ 8.75 (dd, J = 4.0, 1.4 Hz, 1 H), 8.60 (dd, J = 8.4, 1.4 Hz, 1 H), 7.78 (d, J = 7.8 Hz, 1 H), 7.71−7.68 (m, 1 H), 7.62 (d, J = 8.6 Hz, 1 H), 7.53−7.50 (m, 1 H), 7.36−7.31 (m, 4 H), 7.17 (dd, J = 8.6, 1.8 Hz, 1 H), 6.93 (d, J = 7.8 Hz, 1 H), 5.32 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 147.5, 146.2, 139.0, 137.7, 137.1, 134.8, 133.8, 131.4, 130.7, 128.4, 127.7, 126.9, 126.5, 125.2, 124.9, 123.8, 122.5, 114.1, 109.6; ESI-HRMS calcd for C19H15N2S [M + H]+ 303.0950, found 303.0954. 5-(Quinolin-8-ylthio)quinolin-8-amine (3l): Black solid; 29.0 mg, 48% yield; mp 139−140 °C; 1H NMR (400 MHz, CDCl3) δ 9.02 (d, J = 2.8 Hz, 1 H), 8.80 (s, 1 H), 8.18−8.12 (m, 2 H), 7.63 (d, J = 8.4 Hz, 1 H), 7.55 (d, J = 8.0 Hz, 1 H), 7.50−7.45 (m, 2 H), 7.28 (t, J = 7.8 Hz, 1 H), 7.17 (d, J = 8.4 Hz, 1 H), 6.93 (d, J = 7.4 Hz, 1 H), 5.85 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 149.3, 148.3, 147.6, 145.2, 137.1, 136.4, 136.2, 135.1, 129.7, 128.6, 126.8, 124.8, 124.3, 124.2, 122.3, 121.7, 115.3, 107.2; ESI-HRMS calcd for C18H14N3S [M + H]+ 304.0903, found 304.0906. 6-Methyl-5-(phenylthio)quinolin-8-amine (3m): Black liquid; 34.5 mg, 65% yield; 1H NMR (400 MHz, CDCl3) δ 8.80−8.61 (m, 2 H), 7.35 (dd, J = 8.4, 4.2 Hz, 1 H), 7.11 (t, J = 7.6 Hz, 2 H), 7.01 (t, J = 7.2 Hz, 1 H), 6.89 (t, 3 H), 5.19 (s, 2 H), 2.56 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 146.6, 145.5, 145.3, 139.2, 138.0, 134.6, 131.6, 128.8, 125.4, 124.5, 122.5, 112.4, 112.3, 22.1; ESI-HRMS calcd for C16H15N2S [M + H]+ 267.0950, found 267.0948. 6-Methyl-5-(p-tolylthio)quinolin-8-amine (3n): Black liquid; 36.0 mg, 64% yield; 1H NMR (400 MHz, CDCl3) δ 8.75−8.67 (m, 2 H), 7.37 (dd, J = 8.4, 4.0 Hz, 1 H), 6.94 (d, J = 8.0 Hz, 3 H), 6.79 (d, J = 8.0 Hz, 2 H), 5.19 (s, 2 H), 2.57 (s, 3 H), 2.23 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 146.5, 145.3, 145.2, 137.9, 135.6, 134.8, 134.3, 131.6, 129.6, 125.5, 122.4, 113.0, 112.4, 22.1, 20.8; ESI-HRMS calcd for C17H17N2S [M + H]+ 281.1107, found 281.1110.

EXPERIMENTAL SECTION

General Experimental Information. All of the reactions were performed under air atmosphere. Except tosyl hydrazide, other sulfonyl hydrazides18 as well as the substituted 8-aminoquinolines3e,19 used in the experiments were synthesized following a literature process. All other chemical reagents and solvents were obtained from commercial sources and used directly without further treatment. The 1 H and 13C NMR were recorded in a 400 MHz apparatus in CDCl3 or DMSO-d6, and the frequencies for 1H NMR and 13C NMR tests were 400 and 100 MHz, respectively. The chemical shifts are reported in parts per million with TMS as the internal standard. Melting points were tested in an X-4A instrument without correcting the temperature. The HRMS were obtained under an ESI model in a MS spectrometer equipped with TOF analyzer. General Procedure for the C5-Sulfenylation of 8-Aminoquinolines. In a 25 mL round-bottom flask equipped with a condenser, 8-aminoquinoline 1 (0.2 mmol), sulfonyl hydrazide 2 (0.4 mmol), CuI (0.03 mm0l), Na2CO3 (0.6 mmol), and p-xylene (2 mL) were charged. The resulting mixture was stirred at 120 °C for 12 h. Upon completion (TLC), the reaction was allowed to cool down to room temperature, and 5 mL of water was added into the vessel. The heterogeneous mixture was extracted with ethyl acetate (3 × 10 mL). The combined organic phase was dried over Na2SO4. After filtration, the acquired solution was collected, and the solvent was removed at reduced pressure. The acquired residue was subjected to silica gel column chromatography to give pure products by using mixed petroleum ether and dichloromethane (VPET/VDCM = 1:1) as eluent. 5-(p-Tolylthio)quinolin-8-amine (3a): Black liquid; 35.6 mg, 67% yield; 1H NMR (400 MHz, CDCl3) δ 8.75 (dd, J = 4.0, 1.6 Hz, 1 H), 8.60 (dd, J = 8.4, 1.6 Hz, 1 H), 7.72 (d, J = 7.8 Hz, 1 H), 7.39 (dd, J = 8.4, 4.0 Hz, 1 H), 6.98−6.88 (m, 5 H), 5.32 (s, 2 H), 2.23 (s, 3 H); 13 C NMR (100 MHz, CDCl3) δ 147.4, 145.9, 138.9, 137.3, 135.8, 134.9, 134.8, 130.6, 129.6, 126.6, 122.3, 115.1, 109.5, 20.8; ESIHRMS calcd for C16H15N2S [M + H]+ 267.0950, found 267.0956. 5-(Phenylthio)quinolin-8-amine (3b): 12a Black liquid; 30.0 mg, 60% yield; 1H NMR (400 MHz, CDCl3) δ 8.76 (dd, J = 4.0, 1.4 Hz, 1 H), 8.59 (dd, J = 8.4, 1.4 Hz, 1 H), 7.73 (d, J = 7.8 Hz, 1 H), 7.39 (dd, J = 8.4, 4.2 Hz, 1 H), 7.13 (t, J = 7.6 Hz, 2 H), 7.03 (t, J = 7.2 Hz, 1 H), 6.98 (d, J = 7.4 Hz, 2 H), 6.91 (d, J = 7.8 Hz, 1 H), 5.27 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 147.5, 146.1, 139.6, 138.9, 137.7, 134.8, 130.7, 128.8, 126.1, 124.9, 122.4, 114.2, 109.5. 5-((4-Methoxyphenyl)thio)quinolin-8-amine (3c): Black liquid; 33.0 mg, 58% yield; 1H NMR (400 MHz, CDCl3) δ 8.75 (dd, J = 4.2, 1.6 Hz, 1 H), 8.05 (dd, J = 8.2, 1.6 Hz, 1 H), 7.47 (d, J = 8.0 Hz, 1 H), 7.39 (dd, J = 8.2, 4.2 Hz, 1 H), 7.18 (d, J = 8.8 Hz, 2 H), 7.06 (d, J = 8.6 Hz, 1 H), 6.79 (d, J = 8.0 Hz, 2 H), 5.72 (s, 2 H), 3.75 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 158.5, 147.5, 146.2, 136.1, 133.5, 132.7, 130.0, 128.9, 126.7, 121.9, 115.1, 114.8, 55.4; ESI-HRMS calcd for C16H15N2OS [M + H]+ 283.0900, found 283.0904. 5-((4-Fluorophenyl)thio)quinolin-8-amine (3d): Black liquid; 27.5 mg, 51% yield; 1H NMR (400 MHz, CDCl3) δ 8.76 (dd, J = 4.0, 1.4 Hz, 1 H), 8.57 (dd, J = 8.4, 1.4 Hz, 1 H), 7.71 (d, J = 7.8 Hz, 1 H), 7.41 (dd, J = 8.4, 4.2 Hz, 1 H), 7.00−6.96 (m, 2 H), 6.92−6.83 (m, 3 H), 5.33 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 160.9 (d, 1JC−F = 243 Hz), 147.5, 146.1, 138.8, 137.4, 134.6, 134.4, 130.5, 128.2 (d, 3 JC−F = 7 Hz), 122.4, 115.9 (d, 2JC−F = 22 Hz), 114.7, 109.4; ESIHRMS calcd for C15H12FN2S [M + H]+ 271.0700, found 271.0698. 5-((4-Chlorophenyl)thio)quinolin-8-amine (3e): Brown solid; 34.5 mg, 60% yield; mp 123−124 °C; 1H NMR (400 MHz, CDCl3) δ 8.76 (dd, J = 4.0, 1.4 Hz, 1 H), 8.51 (dd, J = 8.4, 1.4 Hz, 1 H), 7.71 (d, J = 7.8 Hz, 1 H), 7.39 (dd, J = 8.4, 4.0 Hz, 1 H), 7.09 (d, J = 8.4 Hz, 2 H), 6.91−6.87 (m, 3 H), 5.32 (s, 2 H); 13C NMR (100 MHz, CDCl3) δ 147.6, 146.4, 139.0, 138.2, 137.8, 134.5, 130.7, 130.5, 128.9, 127.3, 122.6, 113.5, 109.4; ESI-HRMS calcd for C15H12ClN2S [M + H]+ 287.0404, found 287.0410. 5-((4-Bromophenyl)thio)quinolin-8-amine (3f): Brown solid; 34.0 mg, 52% yield; mp 129−130 °C; 1H NMR (400 MHz, CDCl3) δ 8.76 (dd, J = 4.0, 1.4 Hz, 1 H), 8.52 (dd, J = 8.4, 1.4 Hz, 1 H), 7.71 (d, J = 7.8 Hz, 1 H), 7.40 (dd, J = 8.4, 4.0 Hz, 1 H), 7.23 (d, J = 8.6 Hz, 2 11388

DOI: 10.1021/acs.joc.8b01658 J. Org. Chem. 2018, 83, 11385−11391

Note

The Journal of Organic Chemistry 5-((4-Methoxyphenyl)thio)-6-methylquinolin-8-amine (3o): Black solid; 33.0 mg, 57% yield; mp 83−84 °C; 1H NMR (400 MHz, CDCl3) δ 8.76 (dd, J = 8.6, 1.4 Hz, 1 H), 8.69 (dd, J = 4.0, 1.4 Hz, 1 H), 7.38 (dd, J = 8.6, 4.0 Hz, 1 H), 6.92−6.84 (m, 3 H), 6.73− 6.67 (m, 2 H), 5.17 (s, 2 H), 3.71 (s, 3 H), 2.58 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 157.4, 146.5, 145.2, 144.9, 138.0, 134.8, 131.5, 129.8, 127.4, 122.4, 114.6, 112.4, 55.3, 22.2; ESI-HRMS calcd for C17H17N2OS [M + H]+ 297.1056, found 297.1058. 6-Methyl-5-((4-nitrophenyl)thio)quinolin-8-amine (3p): Light yellow solid; 32.0 mg, 51% yield; mp 208−209 °C; 1H NMR (400 MHz, DMSO-d6) δ 8.74 (dd, J = 4.0, 1.6 Hz, 1 H), 8.45 (dd, J = 8.6, 1.6 Hz, 1 H), 8.04 (d, J = 8.0 Hz, 2 H), 7.53 (dd, J = 8.6, 4.0 Hz, 1 H), 7.06 (d, J = 8.0 Hz, 2 H), 6.99 (s, 1 H), 6.58 (s, 2 H), 2.48 (s, 3 H); 13C NMR (100 MHz, DMSO-d6) δ 149.8, 148.4, 146.9, 145.9, 144.9, 137.6, 133.4, 131.2, 125.4, 124.8, 123.6, 111.3, 106.0, 22.1; ESI-HRMS calcd for C16H14N3O2S [M + H]+ 312.0801, found 312.0804. 6-Methyl-5-(naphthalen-2-ylthio)quinolin-8-amine (3q): Red solid; 40.0 mg, 63% yield; mp 170−171 °C; 1H NMR (400 MHz, CDCl3) δ 8.75−8.68 (m, 2 H), 7.69 (d, J = 7.2 Hz, 1 H), 7.62 (d, J = 8.6 Hz, 1 H), 7.48 (d, J = 7.2 Hz, 1 H), 7.36−7.30 (m, 3 H), 7.18− 7.09 (m, 3 H), 6.94 (s, 1 H), 5.23 (s, 2 H), 2.59 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 146.6, 145.6, 145.5, 138.0, 136.8, 134.7, 133.9, 131.6, 131.2, 128.4, 127.7, 126.8, 126.4, 125.0, 124.4, 122.7, 122.6, 112.5, 112.2, 22.2; ESI-HRMS calcd for C20H17N2S [M + H]+ 317.1107, found 317.1108. N-Methyl-5-(p-tolylthio)quinolin-8-amine (3r): Light yellow solid; 12.0 mg, 21% yield; mp 121−122 °C; 1H NMR (400 MHz, CDCl3) δ 8.69 (dd, J = 4.2, 1.6 Hz, 1 H), 8.58 (dd, J = 8.4, 1.6 Hz, 1 H), 7.79 (d, J = 8.0 Hz, 1 H), 7.37 (dd, J = 8.4, 4.2 Hz, 1 H), 6.98−6.84 (m, 4 H), 6.62 (d, J = 8.0 Hz, 1 H), 6.47 (s, 1 H), 3.07 (s, 3 H), 2.23 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 147.5, 146.8, 138.9, 138.1, 136.2, 134.8, 134.6, 130.3, 129.6, 126.3, 122.4, 112.1, 103.8, 29.8, 20.8; ESIHRMS calcd for C17H17N2S [M + H]+ 281.1107, found 281.1106. N-Ethyl-5-(p-tolylthio)quinolin-8-amine (3s): Light yellow solid; 14.5 mg, 25% yield; mp 91−92 °C; 1H NMR (400 MHz, CDCl3) δ 8.70 (dd, J = 4.2, 1.6 Hz, 1 H), 8.58 (d, J = 8.4 Hz, 1 H), 7.77 (d, J = 8.0 Hz, 1 H), 7.38 (dd, J = 8.4, 4.2 Hz, 1 H), 6.98−6.87 (m, 4 H), 6.65 (d, J = 8.0 Hz, 1 H), 6.41 (s, 1 H), 3.39 (q, J = 7.2 Hz, 2 H), 2.23 (s, 3 H), 1.43 (t, J = 7.2 Hz, 3 H); 13C NMR (100 MHz, CDCl3) δ 146.7, 146.4, 138.1, 136.2, 134.7, 130.4, 129.6, 126.2, 122.3, 112.0, 104.2, 37.7, 20.8, 14.5; ESI-HRMS calcd for C18H19N2S [M + H]+ 295.1263, found 295.1262. General Procedure for the N-Acylation of 5-Sulfenylated 8Aminoquinolines 3. Acyl chloride 4 (0.3 mmol) was added dropwise to a solution of compound 3 (0.2 mmol) and Et3N (0.24 mmol) in CH2Cl2 (2 mL) at 0 °C. The mixture was stirred overnight at room temperature. Then the mixture was diluted with CH2Cl2 (10 mL), and the resulting mixture was washed successively with water, saturated NaHCO3 solution, and brine. The organic layer was dried over Na2SO4, and the solvent was then removed under reduced pressure. The resulting residue was purified by silica gel column chromatography eluted with mixted petroleum ether and dichloromethane (VPET/VDCM = 1:1) to afford products 5. N-(5-(p-Tolylthio)quinolin-8-yl)benzamide (5a): White solid; 68.0 mg, 92% yield; mp 170−171 °C; 1H NMR (400 MHz, CDCl3) δ 10.83 (s, 1 H), 8.91 (dd, J = 8.2, 1.0 Hz, 1 H), 8.88−8.82 (m, 2 H), 8.71 (d, J = 8.4 Hz, 1 H), 8.09 (d, J = 7.6 Hz, 2 H), 7.85 (dd, J = 8.0, 0.8 Hz, 1 H), 7.63−7.51 (m, 6 H), 7.54−7.45 (m, 2 H), 7.06−7.01 (m, 4 H), 2.27 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 165.5, 148.4, 139.5, 136.2, 135.6, 135.0, 135.0, 134.9, 133.6, 132,0, 129.9, 129.1, 128.9, 128.5, 127.3, 124.4, 122.3, 116.4, 20.9; ESI-HRMS calcd for C23H19N2OS [M + H]+ 371.1213, found 371.1218. N-(6-Methyl-5-(phenylthio)quinolin-8-yl)benzamide (5b): White solid; 66.0 mg, 89% yield; mp 187−188 °C; 1H NMR (400 MHz, CDCl3) δ 10.84 (s, 1 H), 8.99 (s, 1 H), 8.84−8.77 (m, 2 H), 8.11− 8.07 (m, 2 H), 7.61−7.53 (m, 3 H), 7.46 (dd, J = 8.4, 4.2 Hz, 1 H), 7.14 (t, J = 7.4 Hz, 2 H), 7.04 (t, J = 7.4 Hz, 1 H), 6.94−6.89 (m, 2 H), 2.72 (s, 3 H); 13C NMR (100 MHz, CDCl3) δ 165.6, 147.5, 145.4, 138.5, 138.0, 135.8, 135.2, 134.9, 132.1, 130.7, 129.0, 128.9,

127.4, 125.9, 125.0, 122.7, 120.1, 119.2, 22.6; ESI-HRMS calcd for C23H19N2OS [M + H]+ 371.1213, found 371.1219. N-(6-Methyl-5-((4-nitrophenyl)thio)quinolin-8-yl)acetamide (5c): Yellow solid; 63.5 mg, 90% yield; mp 193−194 °C; 1H NMR (400 MHz, CDCl3) δ 9.93 (s, 1 H), 8.86 (s, 1 H), 8.79 (d, J = 4.0 Hz, 1 H), 8.66 (d, J = 8.0 Hz, 1 H), 7.99 (d, J = 8.0 Hz, 2 H), 7.49 (dd, J = 8.0, 4.0 Hz, 1 H), 6.95 (d, J = 8.0 Hz, 2 H), 2.67 (s, 3 H), 2.40 (s, 3 H); 13 C NMR (100 MHz, CDCl3) δ 169.1, 147.9, 147.7, 146.1, 145.2, 138.0, 136.6, 134.4, 130.2, 125.2, 124.2, 123.0, 119.0, 117.0, 25.2, 22.4; ESI-HRMS calcd for C18H16N3O3S [M + H]+ 354.0907, found 354.0912.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b01658. 1

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H and 13C NMR spectra for products 3 and 5 (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Jie-Ping Wan: 0000-0002-9367-8384 Yunyun Liu: 0000-0002-5553-1672 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (21562024).

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REFERENCES

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