Divergent Synthesis of Allenylsulfonamide and ... - ACS Publications

Oct 11, 2018 - Sadhanendu Samanta and Alakananda Hajra*. Department of Chemistry, Visva-Bharati (A Central University), Santiniketan 731235, India...
0 downloads 0 Views 1MB Size
Download PDF
Article pubs.acs.org/joc

Cite This: J. Org. Chem. 2018, 83, 13157−13165

Divergent Synthesis of Allenylsulfonamide and Enaminonesulfonamide via In(III)-Catalyzed Couplings of Propargylamine and N‑Fluorobenzenesulfonimide Sadhanendu Samanta and Alakananda Hajra*

J. Org. Chem. 2018.83:13157-13165. Downloaded from pubs.acs.org by UNIV OF LOUISIANA AT LAFAYETTE on 11/02/18. For personal use only.

Department of Chemistry, Visva-Bharati (A Central University), Santiniketan 731235, India S Supporting Information *

ABSTRACT: An In(III)-catalyzed facile and controllable method for the synthesis of allenylsulfonamide and enaminonesulfonamide has been achieved by the reaction between propargylamine and N-fluorobenzenesulfonimide (NFSI) under mild conditions. The present protocol is also applicable to the synthesis of tetrasubstituted allenylsulfonamide from triphenyl propargylalcohol. Experimental results suggest that the reaction probably proceeds through the ionic pathway.

■

INTRODUCTION 1

Scheme 1. Protocols for Allenylsulfonamide and Enaminonesulfonamide

2

Allenes and enaminones are the most powerful and versatile synthetic building blocks having broad applications in modern synthetic chemistry. They are widely found in a variety of natural products and pharmaceutical molecules.3 Moreover, allenes have attracted significant interest over the past few years due to their unique cumulene structure, unusual activities, and high reactivity compared to that of alkene and alkyne.4 Allenamide,5 a special class of functionalized allene, has received much attention from the synthetic community due to its prevalence in a large number of natural compounds, marketed drugs, and optoelectronic materials.6 This scaffold is also found in anti-HIV-1 and antihepatitis-B virus agents.7 However, in contrast to their broad applications, the strategies for synthesizing these molecules are limited. Traditionally, allenamides are prepared by the base-induced isomerization,8 Claisen-type sigmatropic rearrangement,9 and aminocyclization of substituted alkynes.10 Allenamides are also synthesized from ynamides.11 Moreover, transition metal-catalyzed coupling between the allenyl halide and amide affords allenamides,12 but it needs prefunctionalization of the starting materials. Recently Zhang et al. reported a Cu-catalyzed radical amination of allenes with N-fluorodiarenesulfonimides to afford allenylsulfonamides (Scheme 1a).13a In addition, the Wang group described the synthesis of α-fluoroallenoate by the reaction between alkynals and N-fluorobenzenesulfonimide (NFSI), where NFSI acts as a fluorine source (Scheme 1b).13b We envisioned that allenylsulfonamides could be directly prepared from propargylamine derivatives by a nucleophilic substitution in the presence of Lewis acids. It is noteworthy, that propargylamines are easily prepared by A3-coupling © 2018 American Chemical Society

reactions.14 These derivatives are also suitable for allene formation via isomerization as well as nucleophilic addition. NFSI is an important reagent that can act as a source of both fluoronium cations (F+) and the nucleophilic imidating agent.15 In recent years, NFSI has been explored in various amination reactions by Liu,16a Zhang,16b Itami,16c and many other groups by using transition-metal catalysts.16 Recently, we have explored indium reagents in various chemical transformations.17f Indium(III)-catalysts are used as a mild and water-tolerant Lewis acid imparting high regio-, stereo-, and chemoselectivity in various organic transformations.17 Compared to the other Lewis acids, indium(III)-compounds have advantages of water stability, recyclability, and operational Received: July 23, 2018 Published: October 11, 2018 13157

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry Table 1. Optimization of the Reaction Conditionsa

entry

catalyst (10 mol %)

base (1 equiv)

solvent (3 mL)

yield of 3a (%)

yield of 4b (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 In(OTf)3 InCl3 In2O3 CuI

Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 Na2CO3 K2CO3 Cs2CO3 NaOH KOtBu Na2CO3 Na2CO3 Na2CO3 Na2CO3

1,2-DCE DCM 1,4-dioxane THF DMF 1,2-DCB toluene CH3CN H2O DCM DCM DCM DCM 1,2-DCE DCM DCM DCM DCM DCM

65 88 trace 21

27 trace trace 46 29 25 57 69 71 12 24 trace 15 86, 83b 49 68 36 trace tracec

In(OTf)3 In(OTf)3

Na2CO3

11 trace trace 78 65 73 71 23 trace trace 49 82

a

Reaction conditions: All reactions were carried out with 0.2 mmol of 1a, 0.24 mmol of 2, 10 mol % catalyst, and 1 equiv of base in 3 mL of solvent for 16 h at 60 °C. bOne drop of H2O was added. cReaction with 20 mol % catalyst and 2 equiv of base at 50 °C.

transformation (Table 1, entries 10−13). The allenylsulfonamide product was formed as a major product in all of the cases, while Na2CO3 was the most effective base to give a satisfactory yield of the product (Table 1, entry 2). Interestingly, the screening of other metal catalysts, such as InCl3, In2O3, and CuI (Table 1, entries 14−16), revealed that the hydroaminated product could be obtained in an excellent yield by using InCl3 as a catalyst in 1,2-DCE solvent (Table 1, entry 14). No further improvement of the yield was observed with the addition of water (Table 1, entry 14). A lower yield of 4b was obtained in the absence of any catalyst or bases, and a trace amount of allenylsulfonamide product was formed without any catalyst (Table 1, entries 17 and 18). No significant increment of the yield was obtained with further increasing the amount of base and catalyst loading (Table 1, entry 19). Other pyrrolidine-, piperidine-, and 1,4-tetrahydroisoquinoline-substituted propargylamines were not effective for this reaction. Finally, the optimized reaction conditions were achieved by using 10 mol % of In(OTf)3 and 1 equiv of Na2CO3 in DCM at 60 °C for 16 h under ambient air to afford the allenylsulfonamide product 3a (Table 1, entry 2), where as 10 mol % InCl3 and 1 equiv of Na2CO3 in 1,2-DCE at 60 °C was found to be the optimized conditions for the hydroaminated product (Table 1, entry 14).

simplicity. Moreover, indium reagents are good to activate alkynes.17a,b To the best of our knowledge, there is no such example for the synthesis of allenylsulfonamide13a and enaminonesulfonamide18 compounds via direct substitution of propargylic derivatives with NFSI. In continuing the development of new protocols for the C−N bond construction,19 herein, we report a regioselective synthesis of allenylsulfonamide and enaminonesulfonamide compounds via a facile indium(III)-catalyzed direct substitution of propargylamine with NFSI under ligand-free and additive-free conditions (Scheme 1c).

■

RESULTS AND DISCUSSION We started our investigations by taking 4-(3-phenyl-1-(ptolyl)prop-2-yn-1-yl)morpholine (1a) as a model substrate, as summarized in Table 1. Initially, we carried out the reaction by employing 1.2 equiv of NFSI as an sulfonamide source with 10 mol % of In(OTf)3 and 1 equiv of Na2CO3 in 1,2-DCE at 60 °C. Gratifyingly, the coupling product, N-(1-phenyl-3-(ptolyl)propa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3a), along with (E)-N-(3-oxo-1-phenyl3-(p-tolyl)prop-1-en-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (4b) were obtained in 65 and 27% yields, respectively, after 16 h (Table 1, entry 1). Encouraged by this initial result, we checked the effect of various common solvents like DCM, 1,4-dioxane, THF, DMF, 1,2-DCB, toluene, CH3CN, and H2O (Table 1, entries 2−9). To our delight, 88% yield of 3a was obtained as a major product in DCM (Table 1, entry 2). However, the hydroaminated product 4b was formed as a major product in other solvents, like THF, DMF, 1,2-DCB, toluene, CH3CN, and H2O (Table 1, entries 4−9). Next, we checked the role of other bases for this

With the optimized reaction conditions in hand, we became interested in exploring the generality of this methodology, and the results are represented in Scheme 2. A series of allenylsulfonamide were obtained under the present reaction 13158

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry Scheme 2. Substrate Scopes of Allenylsulfonamidea

moderate to good yields. However, in the case of the chlorocontaining substrate, the allenylsulfonamide product (3r) was formed along with the enaminonesulfonamide product in a 4:1 ratio. Moreover, the naphthyl-substituted allenes were obtained in good yields (3t−3v). The present methodology is also suitable for butyl-substituted propargylamine (1w). The gram-scale reaction was performed under the normal laboratory setup. The reaction afforded the desired product N-(1-phenyl-3-(p-tolyl)propa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3a) in good yield (80%). This result demonstrated the efficiency and practical applicability of this present protocol. Next we demonstrated the versatility of the enaminonesulfonamide reaction by taking substituted propargylamine derivatives and NFSI in the presence of a catalytic amount of InCl3 in 1,2-DCE (Scheme 3). The reaction of propargylamine Scheme 3. Substrate Scopes of Enaminonesulfonamidea

a

Reaction conditions: 0.2 mmol of 1, 0.24 mmol of 2, in the presence of 10 mol % In(OTf)3, and 1 equiv of Na2CO3 in 3 mL of DCM at 60 °C for 16 h. bA 5 mmol scale. cReaction time, 20 h. dReaction time, 28 h. Bs = benzenesulfonyl.

a Reaction conditions: 0.2 mmol of 1, 0.24 mmol of 2, in the presence of 10 mol % InCl3, and 1 equiv of Na2CO3 in 3 mL of 1,2-DCE at 60 °C for 12 h. Bs = benzenesulfonyl.

conditions in good to excellent yields with high selectivity (3a−3w). Propargylamines with electron-donating substituents, like −Me, −OMe, −OEt, −dioxo, and a bulky tert-butyl group, on the phenyl ring usually provided the allenylsulfonamide products (3a−3m) in moderate to good yields. Notably, the para-methyl (1a), meta-methyl (1h), and sterically hindered ortho-methyl-substituted propargylamine (1i) afforded the product in high yields, illustrating that the steric hindrance of substituents on the phenyl ring did not have a strong influence for this kind of reaction. The structure of N(1-phenyl-3-(o-tolyl)propa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3i) was confirmed by X-ray crystallography, which further suggested that two phenyl groups are in the cis-orientation.20a Similarly, substrates 1b and 1j bearing para-methoxy and ortho-methoxy-substituents on the phenyl part reacted smoothly to give the desired products selectively in excellent yields. Furthermore, some disubstituted propargylamine (1k−1o) were also examined and successfully gave the desired products without any difficulties (3k−3o). Strong electron-withdrawing groups containing propargylamines also reacted well under the present reaction conditions (3n and 3o). Propargylamine bearing a halogen substitution on the phenyl ring afforded the desired products (3p−3s) in

with electron-donating or -withdrawing groups in the phenyl ring proceeded smoothly, providing the hydroaminated products in good to excellent yields (4a−4e). X-ray crystallographic analysis was performed to confirm the structure of the E-isomeric product 4c.20b The strong electron-withdrawing substituent, such as cyano-containing propargyl substrate 1f, could be well tolerated (4f). The naphthyl-substituted propargylamine also afforded the product in excellent yield (4g, 90%). However, the hydroxy and alkyl-substituted substrates (1k and 1l) did not provide any product under the present reaction conditions. Furthermore, the scope of the reaction was extended for the synthesis of enaminones via the desulfonylation of the enaminonesulfonamides (Scheme 4).21 Intriguingly, the Eenaminone product 5 was obtained in 73% yield. In order to investigate the mechanistic pathway of this reaction, few control experiments were carried out (Scheme 5). In the presence of radical scavengers, like 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 2,6-di-tert-butyl-4-methyl phenol (BHT), and p-benzoquinone (BQ), the reactions proceeded well in equal ease, which signifies that the reaction probably proceeds through a nonradical pathway (eq A). The reaction was also carried out by taking (PhSO2)2NH instead of NFSI 13159

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry

propargylic carbocationic intermediate (eq D). We have carried out the reaction taking allenylsulfonamide as the starting material under the optimized reaction conditions, but the formation of the enaminonesulfonamide product was not observed; the starting material remained unchanged. This result suggests that allenylsulfonamide was not an intermediate during the formation of enaminonesulfonamide (eq E). A plausible mechanism is proposed for this transformation on the basis of our previous literature reports17,22 and experimental results, as outlined in Scheme 6. Initially, in the presence of a base and the In(III)-catalyst, the carbocationic intermediate A is formed from propargylamine 1a through the elimination of morpholine. Nucleophilic addition of NFSI through its N-center to intermediate A affords allenylsulfonamide product 3a. F+ might be released with the morpholine anion. The existence of electron-donating substituents on the phenyl ring is beneficial for stabilizing the propargylic carbocationic intermediate. On the other hand, hydrolysis23 of intermediate A forms the propargylalcohol B. Subsequently NFSI reacts in the alkyne part of intermediate B to form intermediate C. Finally, the allylic alcohol intermediate C is oxidized in the presence of F+ to produce the enaminonesulfonamide 4b via elimination of HF.

Scheme 4. Desulfonylation of Enaminonesulfonamide

Scheme 5. Control Experiments

■

CONCLUSION In summary, we have developed a divergent method for the synthesis of allenylsulfonamides and enaminonesulfonamides with excellent regioselectivity. Mild reaction conditions, excellent selectivity, high yields, and usage of a water-stabilized In(III)-catalyst are the notable advantages of this methodology. To the best of our knowledge, this is the first report for the synthesis of allenylsulfonamide and enaminonesulfonamide compounds via direct reaction of propargylamines with NFSI. The present methodology is also applicable for the synthesis of tetrasubstituted allenylsulfonamide. We believe that the present methodology opens a new door for the synthesis of allenylsulfonamides in organic synthesis, medicinal chemistry, as well as in material sciences.

under the optimized reaction conditions, but no desired product was obtained (eq B). This experiment suggests that the reaction did not proceed through the formation of (PhSO2)2NH by the decomposition of NFSI. When the reaction between triphenyl propargylalcohol (7) and NFSI (2) was carried out, the corresponding tetrasubstituted allenylsulfonamide product 8 was obtained in 85% yield (eq C), whereas propargylalcohol (9) did not afford any product, which indicates that the amine or hydroxyl group does not play as a directing group, rather it facilitates the formation of the

■

EXPERIMENTAL SECTION

General Information. All reagents were purchased from commercial sources and used without further purification. 1H NMR spectra were determined on a 400 MHz spectrometer as solutions in CDCl3. Chemical shifts are expressed in parts per million (δ); the signals are reported as s (singlet), d (doublet), t (triplet), and m

Scheme 6. Plausible Mechanistic Pathway

13160

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry (multiplet); and the coupling constants (J) are given in Hz. 13C{1H} NMR spectra were recorded at 100 MHz in CDCl3 solution. Chemical shifts as an internal standard are referenced to CDCl3 (δ = 7.26 for 1H and δ = 77.16 for 13C{1H} NMR). TLC was done on a silica gel-coated glass slide. All solvents were dried and distilled before use. Commercially available solvents were freshly distilled before the reaction. All reactions involving moisture sensitive reactants were executed using oven-dried glassware. Typical Experimental Procedure for the Synthesized Compounds (3a−3w, and 8). A mixture of propargylamine (0.2 mmol, 58.2 mg) (1a), indium(III)-trifluoromethanesulfonate (10 mol %, 11.2 mg), and sodium carbonate (1 equiv, 21.2 mg) was taken in an oven-dried reaction tube. Then, dichloromethane (3 mL) was added to it, and the reaction was stirred at room temperature for a few seconds. Then, NFSI (1.2 equiv, 75.6 mg) was added to it and stirred at 60 °C with a reflux condenser carrying a CaCl2 guard tube for 16 h. After completion of the reaction (TLC), the reaction was cooled to room temperature and extracted with dichloromethane. The organic phase was dried over anhydrous Na2SO4. The crude residue was obtained after evaporating the solvent in vacuum and was purified by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (92:8) as an eluting solvent to afford the pure product (3a) (88 mg, 88%) as a white solid. N-(1-Phenyl-3-(p-tolyl)propa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3a). White solid (88%, 88 mg). Rf = 0.50 (PE:EA = 92:8). mp 129−130 °C. 1H NMR (400 MHz, CDCl3): δ 7.92 (s, 4H), 7.61−7.55 (m, 2H), 7.48−7.47 (m, 2H), 7.37−7.32 (m, 4H), 7.28−7.26 (m, 2H), 7.23−7.22 (m, 3H), 7.15 (d, J = 8.0 Hz, 2H), 6.38 (s, 1H), 2.35 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.1, 139.0, 134.0, 132.9, 129.8, 129.0, 128.9, 128.8, 128.5, 128.4, 128.3, 128.2, 126.4, 111.5, 103.0, 21.4. Anal. Calcd for C28H23NO4S2: C, 67.05; H, 4.62; N, 2.79%. Found: C, 67.26; H, 4.66; N, 2.71%. N-(3-(4-Methoxyphenyl)-1-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3b). Brown gummy mass (89%, 92 mg). Rf = 0.55 (PE:EA = 93:7). 1H NMR (400 MHz, CDCl3, δ): 7.92 (s, 4H), 7.60−7.55 (m, 2H), 7.49−7.44 (m, 2H), 7.37−7.34 (m, 4H), 7.32−7.30 (m, 2H), 7.23−7.21 (m, 3H), 6.87 (d, J = 8.8 Hz, 2H), 6.37 (s, 1H), 3.80 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.8, 160.2, 139.7, 138.7, 133.9, 133.0, 129.7, 129.0, 128.8, 128.5, 128.3, 126.4, 123.3, 114.5, 111.4, 102.7, 55.4. Anal. Calcd for C28H23NO5S 2: C, 64.97; H, 4.48; N, 2.71%. Found: C, 64.81; H, 4.54; N, 2.65%. N-(3-(Benzo[d][1,3]dioxol-5-yl)-1-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3c). Yellow gummy mass (81%, 86 mg). Rf = 0.55 (PE:EA = 92:8). 1H NMR (400 MHz, CDCl3, δ): 7.94 (d, J = 7.6 Hz, 4H), 7.59 (s, 2H), 7.50−7.46 (m, 2H), 7.42−7.37 (m, 2H), 7.35−7.32 (m, 2H), 7.24−7.21 (m, 3H), 6.94 (d, J = 1.2 Hz, 1H), 6.79−6.74 (m, 2H), 6.32 (s, 1H), 5.95−5.94 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.8, 148.44, 148.41, 135.0, 134.0, 132.8, 129.0, 128.8, 128.5, 128.4, 126.4, 125.0, 122.7, 111.6, 108.6, 108.1, 103.0, 101.4. Anal. Calcd for C28H21NO6S 2: C, 63.26; H, 3.98; N, 2.63%. Found: C, 63.51; H, 3.94; N, 2.70%. N-(3-Phenyl-1-(p-tolyl)propa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3d). Brown solid (74%, 74 mg). Rf = 0.45 (PE:EA = 91:9). mp 130−131 °C. 1H NMR (400 MHz, CDCl3, δ): 7.94−7.90 (m, 4H), 7.64−7.52 (m, 2H), 7.49−7.46 (m, 2H), 7.36− 7.29 (m, 7H), 7.25 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 8.0 Hz, 2H), 6.36 (s, 1H), 2.32 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.0, 138.5, 134.0, 133.9, 131.4, 129.8, 129.3, 129.0, 128.88, 128.84, 128.7, 128.4, 126.3, 111.7, 103.0, 21.3. Anal. Calcd for C28H23NO4S2: C, 67.05; H, 4.62; N, 2.79%. Found: C, 67.23; H, 4.57; N, 2.73%. N-(1-(4-Methoxyphenyl)-3-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3e). Brown gummy mass (83%, 85 mg). Rf = 0.45 (PE:EA = 92:8). 1H NMR (400 MHz, CDCl3, δ): 7.91 (d, J = 6.8 Hz, 4H), 7.64−7.52 (m, 2H), 7.49−7.45 (m, 2H), 7.37−7.27 (m, 9H), 6.78−6.75 (m, 2H), 6.36 (s, 1H), 3.79 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.7, 159.9, 134.0, 133.3, 131.6, 129.07, 129.02, 128.9, 128.8, 128.3, 127.8, 125.0, 114.0, 111.6, 103.0, 55.5. Anal. Calcd for C28H23NO 5S2: C, 64.97; H, 4.48; N, 2.71%. Found: C, 65.17; H, 4.44; N, 2.78%.

N-(1-(4-Ethoxyphenyl)-3-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3f). White gummy mass (78%, 82 mg). Rf = 0.45 (PE:EA = 93:7). 1H NMR (400 MHz, CDCl3, δ): 7.94 (d, J = 7.6 Hz, 4H), 7.63−7.49 (m, 4H), 7.40−7.27 (m, 9H), 6.79−7.75 (m, 2H), 6.39 (s, 1H), 4.06−4.01 (m, 2H), 1.42 (t, J = 7.2 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.7, 159.3, 134.0, 133.9, 131.7, 129.06, 129.03, 128.8, 128.7, 128.3, 127.9, 124.8, 114.6, 111.6, 103.0, 63.6, 14.8. Anal. Calcd for C29H 25NO5S2: C, 65.52; H, 4.74; N, 2.63%. Found: C, 65.69; H, 4.70; N, 2.69%. N-(1-(4-(tert-Butyl)phenyl)-3-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3g). Brown gummy mass (77%, 83 mg). Rf = 0.40 (PE:EA = 92:8). 1H NMR (400 MHz, CDCl3, δ): 7.91 (t, J = 8.4 Hz, 4H), 7.63−7.58 (m, 1H), 7.55−7.50 (m, 1H), 7.48−7.43 (m, 2H), 7.38−7.33 (m, 4H), 7.31−7.22 (m, 7H), 6.39 (s, 1H), 1.29 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.1, 151.6, 136.5, 133.8, 131.5, 129.7, 129.0, 128.8, 128.7, 128.4, 126.2, 125.5, 111.7, 102.9, 34.7, 31.3. Anal. Calcd for C31H29NO 4S2: C, 68.48; H, 5.38; N, 2.58%. Found: C, 68.26; H, 5.43; N, 2.53%. N-(3-Phenyl-1-(m-tolyl)propa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3h). Yellow gummy mass (70%, 70 mg). Rf = 0.50 (PE:EA = 90:10). 1H NMR (400 MHz, CDCl3, δ): 7.93 (d, J = 7.6 Hz, 4H), 7.64−7.60 (m, 1H), 7.55−7.46 (m, 3H), 7.38−7.29 (m, 7H), 7.17−7.03 (m, 4H), 6.42 (s, 1H), 2.20 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.2, 138.9, 138.2, 134.0, 133.9, 132.5, 131.4, 129.3, 129.0, 128.8, 128.7, 128.49, 128.47, 128.3, 126.9, 123.7, 103.0, 21.5. Anal. Calcd for C28H 23NO4S2: C, 67.05; H, 4.62; N, 2.79%. Found: C, 66.82; H, 4.65; N, 2.88%. N-(1-Phenyl-3-(o-tolyl)propa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3i). White solid (79%, 79 mg). Rf = 0.55 (PE:EA = 89:11). mp 142−143 °C. 1H NMR (400 MHz, CDCl3, δ): 7.90−7.87 (m, 4H), 7.64−7.60 (m, 1H), 7.49−7.38 (m, 6H), 7.25− 7.24 (m, 5H), 7.20−7.14 (m, 3H), 6.57 (s, 1H), 2.22 (s, 3H). 13 C{1H} NMR (100 MHz, CDCl3, δ): 210.3, 139.4, 136.1, 134.0, 132.8, 130.8, 129.7, 129.1, 129.0, 128.9, 128.6, 128.5, 128.4, 126.7, 126.3, 111.1, 100.5, 19.8. Anal. Calcd for C28H23NO4S2: C, 67.05; H, 4.62; N, 2.79%. Found: C, 67.22; H, 4.58; N, 2.86%. N-(3-(2-Methoxyphenyl)-1-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3j). Light yellow gummy mass (80%, 82 mg). Rf = 0.45 (PE:EA = 91:9). 1H NMR (400 MHz, CDCl3, δ): 7.85−7.81 (m, 4H), 7.52−7.48 (m, 1H), 7.43−7.34 (m, 4H), 7.30−7.28 (m, 2H), 7.22−7.18 (m, 3H), 7.15−7.13 (m, 3H), 6.86−6.79 (m, 2H), 6.71 (s, 1H), 3.74 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.9, 156.9, 133.9, 133.7, 133.3, 130.2, 129.9, 129.0, 128.8, 128.7, 128.4, 128.1, 126.3, 121.1, 119.7, 111.0, 97.7, 55.7. Anal. Calcd for C28H23NO5S2: C, 64.97; H, 4.48; N, 2.71%. Found: C, 64.74; H, 4.45; N, 2.65%. N-(1,3-Di-p-tolylpropa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3k). Yellow gummy mass (82%, 84 mg). Rf = 0.45 (PE:EA = 91:9). 1H NMR (400 MHz, CDCl3, δ): 7.94−7.89 (m, 4H), 7.61−7.55 (m, 2H), 7.48−7.45 (m, 2H), 7.35−7.34 (m, 2H), 7.26−7.24 (m, 4H), 7.14 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 8.4 Hz, 2H), 6.33 (s, 1H), 2.34 (s, 3H), 2.32 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.8, 138.9, 138.4, 134.0, 133.9, 130.0, 129.7, 129.2, 129.0, 128.7, 128.4, 128.3, 126.3, 111.5, 102.9, 21.4, 21.3. Anal. Calcd for C29H25NO4S2: C, 67.57; H, 4.89; N, 2.72%. Found: C, 67.36; H, 4.95; N, 2.81%. N-(1-(4-Methoxyphenyl)-3-(p-tolyl)propa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3l). Light yellow gummy mass (78%, 82 mg). Rf = 0.50 (PE:EA = 89:11). 1H NMR (400 MHz, CDCl3, δ): 7.91 (t, J = 8.0 Hz, 4H), 7.60−7.52 (m, 2H), 7.46 (t, J = 7.2 Hz, 2H), 7.33 (t, J = 6.8 Hz, 2H), 7.29−7.24 (m, 4H), 7.14 (d, J = 8.0 Hz, 2H), 6.76 (d, J = 8.8 Hz, 2H), 6.32 (s, 1H), 3.78 (s, 3H), 2.34 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.5, 159.9, 138.9, 133.8, 129.7, 129.0, 128.87, 128.80, 128.6, 128.3, 127.8, 125.2, 114.0, 111.3, 102.9, 55.5, 21.4. Anal. Calcd for C29H 25NO5S2: C, 65.52; H, 4.74; N, 2.63%. Found: C, 65.72; H, 4.69; N, 2.73%. N-(1,3-Bis(4-methoxyphenyl)propa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3m). Brown gummy mass (71%, 77 mg). Rf = 0.50 (PE:EA = 90:10). 1H NMR (400 MHz, CDCl3, δ): 7.93−7.88 (m, 4H), 7.60−7.53 (m, 2H), 7.47−7.46 (m, 2H), 7.36−7.34 (m, 2H), 7.30−7.25 (m, 4H), 6.87−6.85 (m, 2H), 13161

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry

7.22 (m, 5H), 6.58 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.8, 139.6, 138.7, 134.0, 133.5, 133.4, 132.7, 129.0, 128.9, 128.8, 128.59, 128.56, 128.1, 128.0, 127.9, 126.7, 126.6, 126.4, 125.4, 111.9, 103.4. Anal. Calcd for C31H23NO4S2: C, 69.25; H, 4.31; N, 2.61%. Found: C, 69.01; H, 4.37; N, 2.69%. N-(1-(4-(tert-Butyl)phenyl)-3-(naphthalen-2-yl)propa-1,2-dien-1yl)-N-(phenylsulfonyl)benzenesulfonamide (3u). Brown gummy mass (88%, 104 mg). Rf = 0.50 (PE:EA = 90:10). 1H NMR (400 MHz, CDCl3, δ): 7.95−7.88 (m, 4H), 7.80−7.76 (m, 3H), 7.68 (s, 1H), 7.61−7.59 (m, 2H), 7.47−7.45 (m, 5H), 7.31 (d, J = 8.4 Hz, 2H), 7.25−7.23 (m, 4H), 6.54 (s, 1H), 1.28 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.6, 151.7, 134.0, 133.8, 133.5, 133.4, 129.7, 129.08, 129.04, 128.9, 128.8, 128.7, 128.1, 127.9, 126.7, 126.6, 126.2, 125.58, 125.51, 111.9, 103.3, 34.7, 31.3. Anal. Calcd for C35H31NO4S2: C, 70.80; H, 5.26; N, 2.36%. Found: C, 70.58; H, 5.20; N, 2.43%. N-(3-(Naphthalen-1-yl)-1-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3v). Brown gummy mass (87%, 93 mg). Rf = 0.50 (PE:EA = 89:11). 1H NMR (400 MHz, CDCl3, δ): 7.93−7.87 (m, 4H), 7.85−7.77 (m, 3H), 7.66−7.63 (m, 1H), 7.60−7.58 (m, 1H), 7.55−7.43 (m, 7H), 7.29−7.22 (m, 4H), 7.12 (s, 1H), 6.99 (t, J = 6.8 Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3, δ): 211.0, 139.1, 134.0, 133.9, 133.6, 132.8, 130.9, 129.5, 129.1, 128.9, 128.6, 128.5, 127.7, 127.6, 126.9, 126.4, 126.2, 125.8, 123.6, 110.9, 100.0. Anal. Calcd for C31H23NO4S2: C, 69.25; H, 4.31; N, 2.61%. Found: C, 69.52; H, 4.35; N, 2.52%. N-(1-(4-Methoxyphenyl)hepta-1,2-dien-3-yl)-N-(phenylsulfonyl)benzenesulfonamide (3w). Yellow oil (84%, 83 mg). Rf = 0.45 (PE:EA = 93:7). 1H NMR (400 MHz, CDCl3, δ): 7.94 (d, J = 5.2 Hz, 4H), 7.61−7.56 (m, 2H), 7.44 (br s, 4H), 7.21−7.18 (m, 2H), 6.85− 6.83 (m, 2H), 5.92 (t, J = 4.0 Hz, 1H), 3.79 (s, 3H), 2.45−2.39 (m, 2H), 1.44−1.32 (m, 4H), 0.86 (t, J = 7.2 Hz, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 207.3, 159.8, 133.8, 129.9, 129.3, 128.9, 128.5, 124.3, 114.3, 110.6, 101.0, 55.4, 34.0, 28.8, 22.1, 14.0. Anal. Calcd for C26H27NO5S2: C, 62.76; H, 5.47; N, 2.81%. Found: C, 62.54; H, 5.43; N, 2.88%. N-(Phenylsulfonyl)-N-(1,3,3-triphenylpropa-1,2-dien-1-yl)benzenesulfonamide (8). White solid (85%, 95 mg). Rf = 0.45 (PE:EA = 88:12). mp 163−164 °C. 1H NMR (400 MHz, CDCl3, δ): 7.88−7.86 (m, 4H), 7.53 (t, J = 8.0 Hz, 2H), 7.44 (s, 10H), 7.38− 7.36 (m, 2H), 7.31−7.23 (m, 7H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.0, 139.4, 134.4, 134.3, 133.7, 133.0, 129.4, 129.1, 129.0, 128.9, 128.8, 128.7, 128.6, 128.5, 128.4, 128.3, 126.6, 119.0, 110.7. Anal. Calcd for C33H25NO4S2: C, 70.32; H, 4.47; N, 2.48%. Found: C, 70.51; H, 4.43; N, 2.43%. Typical Experimental Procedure for the Synthesized Compounds (4a−4j). A mixture of propargylamine (0.2 mmol, 58.2 mg) (1a), indium(III)-chloride (10 mol %, 4.4 mg), and sodium carbonate (1 equiv, 21.2 mg) was taken in an oven-dried reaction tube. Then 1,2-dichloroethane (2 mL) was added to it and stirred at room temperature for a few seconds. Then NFSI (1.2 equiv, 75.6 mg) was added to it and stirred at 60 °C for 12 h. After completion of the reaction (TLC), the reaction was cooled to room temperature and extracted with dichloromethane. The organic phase was dried over anhydrous Na2SO4. The crude residue was obtained after evaporating the solvent in vacuum and was purified by column chromatography on silica gel using a mixture of petroleum ether and ethyl acetate (91:9) as an eluting solvent to afford the pure product (4b) (88 mg, 86%) as a yellow solid. (E)-N-(3-Oxo-1,3-diphenylprop-1-en-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (4a). White solid (89%, 89 mg). Rf = 0.45 (PE:EA = 93:7). mp 110−111 °C. 1H NMR (400 MHz, CDCl3, δ): 7.89−7.84 (m, 6H), 7.62−7.58 (m, 2H), 7.46−7.40 (m, 5H), 7.32− 7.29 (m, 4H), 7.18−7.14 (m, 1H), 7.06−7.02 (m, 2H), 6.28 (s, 1H). 13 C{1H} NMR (100 MHz, CDCl3, δ): 192.6, 143.9, 139.4, 136.3, 134.2, 134.0, 133.6, 131.7, 130.2, 130.0, 129.3, 129.0, 128.9, 128.7, 128.2. Anal. Calcd for C27H21NO5S2: C, 64.40; H, 4.20; N, 2.78%. Found: C, 64.56; H, 4.23; N, 2.73%. (E)-N-(3-Oxo-1-phenyl-3-(p-tolyl)prop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4b). Yellow solid (86%, 88

6.76−6.74 (m, 2H), 6.32 (s, 1H), 3.80 (s, 3H), 3.78 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 209.1, 160.2, 159.8, 133.9, 129.7, 129.3, 129.0, 128.8, 127.8, 125.4, 123.8, 114.5, 114.0, 111.3, 102.6, 55.5. Anal. Calcd for C29H25NO6S2: C, 63.60; H, 4.60; N, 2.56%. Found: C, 63.78; H, 4.57; N, 2.50%. N-(1-(4-Methoxyphenyl)-3-(3-nitrophenyl)propa-1,2-dien-1-yl)N-(phenylsulfonyl)benzenesulfonamide (3n). Yellow solid (82%, 92 mg). Rf = 0.50 (PE:EA = 85:15). mp 137−138 °C. 1H NMR (400 MHz, CDCl3, δ): 8.12−8.10 (m, 2H), 7.98−7.97 (m, 4H), 7.79 (d, J = 8.0 Hz, 1H), 7.51−7.47 (m, 5H), 7.42 (br s, 2H), 7.25−7.23 (m, 2H), 6.77−6.75 (m, 2H), 6.40 (s, 1H), 3.78 (m, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.7, 160.3, 148.7, 134.3, 134.23, 134.20, 133.8, 133.7, 130.0, 129.0, 128.0, 124.0, 123.3, 122.9, 114.2, 112.7, 101.1, 55.5%. Anal. Calcd for C28H22N2O7S2: C, 59.78; H, 3.94; N, 4.98%. Found: C, 59.59; H, 3.97; N, 4.94%. N-(3-(4-Cyanophenyl)-1-(4-methoxyphenyl)propa-1,2-dien-1yl)-N-(phenylsulfonyl)benzenesulfonamide (3o). White solid (79%, 85 mg). Rf = 0.45 (PE:EA = 90:10). mp 145−146 °C. 1H NMR (400 MHz, CDCl3, δ): 7.94 (br s, 4H), 7.60−7.58 (m, 4H), 7.50−7.44 (m, 4H), 7.39 (br s, 2H), 7.25−7.22 (m, 2H), 6.77−6.75 (m, 2H), 6.35 (s, 1H), 3.78 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 211.3, 160.3, 136.5, 134.1, 132.7, 128.95, 128.94, 128.7, 127.9, 123.9, 118.6, 114.1, 112.6, 111.9, 101.6, 55.4. Anal. Calcd for C29H22N 2O5S2: C, 64.19; H, 4.09; N, 5.16%. Found: C, 64.05; H, 4.13; N, 5.22%. N-(3-(2-Bromo-5-methoxyphenyl)-1-phenylpropa-1,2-dien-1-yl)N-(phenylsulfonyl)benzenesulfonamide (3p). White solid (78%, 92 mg). Rf = 0.45 (PE:EA = 93:7). mp 161−162 °C. 1H NMR (400 MHz, CDCl3, δ): 7.96 (br s, 4H), 7.63 (br s, 2H), 7.53 (br s, 2H), 7.44−7.40 (m, 5H), 7.32−7.28 (m, 4H), 6.76−6.73 (m, 2H), 3.74 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 211.1, 159.3, 134.4, 134.1, 133.7, 132.4, 131.4, 129.1, 129.0, 128.7, 128.6, 126.4, 118.4, 114.0, 113.2, 112.2, 102.3, 55.8. Anal. Calcd for C28H22BrNO 5S2: C, 56.38; H, 3.72; N, 2.35%. Found: C, 56.21; H, 3.76; N, 2.43%. N-(3-(2-Bromo-4,5-dimethoxyphenyl)-1-phenylpropa-1,2-dien1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3q). White solid (71%, 88 mg). Rf = 0.45 (PE:EA = 92:8). mp 173−174 °C. 1H NMR (400 MHz, CDCl3, δ): 7.91 (t, J = 8.4 Hz, 4H), 7.64−7.58 (m, 2H), 7.49−7.40 (m, 4H), 7.37−7.34 (m, 2H), 7.28 (s, 1H), 7.24 (t, J = 2.4 Hz, 3H), 6.93 (s, 1H), 6.62 (s, 1H), 3.83 (s, 3H), 3.75 (s, 3H). 13 C{1H} NMR (100 MHz, CDCl3, δ): 210.6, 150.3, 149.1, 139.8, 134.3, 134.1, 132.7, 129.1, 128.9, 128.6, 126.4, 122.7, 115.2, 114.0, 112.0, 111.5, 102.2, 56.4, 56.3. Anal. Calcd for C29H24BrNO6S2: C, 55.59; H, 3.86; N, 2.24%. Found: C, 55.81; H, 3.81; N, 2.30%. (E)-N-(3-(4-Chlorophenyl)-3-oxo-1-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide Compound with N-(3-(4Chlorophenyl)-1-phenylpropa-1,2-dien-1-yl)-N-(phenylsulfonyl)benzenesulfonamide (3r + 4d). Yellow gummy mass (64%, 135 mg). Rf = 0.60 (PE:EA = 93:7). 1H NMR (400 MHz, CDCl3, δ): 7.88 (d, J = 7.6 Hz, 4H), 7.83−7.81 (m, 1H), 7.74−7.72 (m, 0.5H), 7.59−7.52 (m, 3H), 7.43−7.37 (m, 4H), 7.30−7.25 (m, 7H), 7.23−7.15 (m, 4H), 6.99 (t, J = 8.0 Hz, 0.5H), 6.31 (s, 1H), 6.18 (s, 0.2H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.4, 191.5, 144.4, 140.0, 139.3, 134.7, 134.6, 134.3, 134.1, 133.9, 132.4, 131.1, 130.7, 130.2, 129.8, 129.5, 129.3, 129.1, 129.0, 128.96, 128.91, 128.69, 128.62, 128.3, 127.7, 126.4, 112.0, 102.1. Anal. Calcd for C27H20ClNO 4S2: C, 62.12; H, 3.86; N, 2.68%. Found: C, 62.31; H, 3.82; N, 2.77%. N-(3-(4-Fluorophenyl)-1-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3s). Yellow gummy mass (73%, 70 mg). Rf = 0.45 (PE:EA = 92:8). 1H NMR (400 MHz, CDCl3, δ): 7.93 (d, J = 7.6 Hz, 4H), 7.63−7.57 (m, 2H), 7.48−7.43 (m, 2H), 7.37−7.32 (m, 6H), 7.24−7.22 (m, 3H), 7.02 (t, J = 8.8 Hz, 2H), 6.38 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 210.0, 163.0 (JC−F = 243.0 Hz), 134.0, 132.6, 130.1, 130.0, 129.0, 128.8, 128.5, 127.3 (JC−F = 4.0 Hz), 126.4, 116.3, 116.0, 111.9, 102.1. Anal. Calcd for C27H20FNO4S2: C, 64.14; H, 3.99; N, 2.77%. Found: C, 63.97; H, 4.04; N, 2.83%. N-(3-(Naphthalen-2-yl)-1-phenylpropa-1,2-dien-1-yl)-N(phenylsulfonyl)benzenesulfonamide (3t). Yellow solid (84%, 90 mg). Rf = 0.45 (PE:EA = 91:9). mp 191−192 °C. 1H NMR (400 MHz, CDCl3, δ): 7.93 (br s, 4H), 7.80−7.78 (m, 3H), 7.69 (s, 1H), 7.62−7.59 (m, 2H), 7.50−7.46 (m, 5H), 7.42−7.37 (m, 2H), 7.29− 13162

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry mg). Rf = 0.45 (PE:EA = 91:9). mp 139−140 °C. 1H NMR (400 MHz, CDCl3, δ): 7.89−7.86 (m, 4H), 7.78−7.76 (m, 2H), 7.61−7.57 (m, 2H), 7.45−7.41 (m, 4H), 7.32−7.30 (m, 2H), 7.19−7.14 (m, 1H), 7.12 (d, J = 8.0 Hz, 2H), 7.05 (t, J = 8.0 Hz, 2H), 6.26 (s, 1H), 2.31 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 192.0, 144.6, 143.2, 139.4, 134.1, 133.8, 132.0, 130.2, 129.8, 129.5, 129.4, 129.0, 128.9, 128.2, 21.8. HRMS (ESI-TOF) (m/z): [M + Na]+ Calcd for C28H23NO5S2Na, 540.0910; found, 540.0913. (E)-N-(3-(4-Fluorophenyl)-3-oxo-1-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4c). White solid (87%, 90 mg). Rf = 0.50 (PE:EA = 92:8). mp 146−147 °C. 1H NMR (400 MHz, CDCl3, δ): 7.88−7.85 (m, 6H), 7.63−7.59 (m, 2H), 7.46−7.42 (m, 4H), 7.28−7.26 (m, 2H), 7.19−7.14 (m, 1H), 7.05−7.02 (m, 2H), 6.97−6.93 (m, 2H), 6.23 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 191.2, 165.9 (JC−F = 255.0 Hz), 144.0, 139.4, 134.3, 134.0, 132.1, 132.0, 131.4, 130.2, 130.1, 129.1, 128.9, 128.3, 115.9 (JC−F = 22.0 Hz). Anal. Calcd for C27H20FNO5S2: C, 62.18; H, 3.87; N, 2.69%. Found: C, 62.37; H, 3.89; N, 2.75%. (E)-N-(3-(4-Chlorophenyl)-3-oxo-1-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4d). Yellow solid (78%, 83 mg). Rf = 0.50 (PE:EA = 90:10). mp 143−144 °C. 1H NMR (400 MHz, CDCl3, δ): 7.82 (d, J = 7.6 Hz, 4H), 7.73 (d, J = 8.8 Hz, 2H), 7.57 (t, J = 7.6 Hz, 2H), 7.40 (t, J = 8.0 Hz, 4H), 7.23−7.20 (m, 4H), 7.13 (t, J = 7.6 Hz, 1H), 7.00 (t, J = 8.0 Hz, 2H), 6.18 (s, 1H). 13 C{1H} NMR (100 MHz, CDCl3, δ): 191.5, 144.4, 140.0, 139.3, 134.6, 134.3, 133.9, 131.1, 130.7, 130.2, 129.1, 129.0, 128.9, 128.3. Anal. Calcd for C27H20ClNO5S2: C, 60.28; H, 3.75; N, 2.60%. Found: C, 60.11; H, 3.69; N, 2.71%. (E)-N-(3-(4-Bromophenyl)-3-oxo-1-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4e). White solid (91%, 105 mg). Rf = 0.45 (PE:EA = 91:9). mp 152−153 °C. 1H NMR (400 MHz, CDCl3, δ): 7.88−7.85 (m, 4H), 7.71−7.68 (m, 2H), 7.60 (t, J = 7.6 Hz, 2H), 7.43 (t, J = 8.4 Hz, 6H), 7.28−7.26 (m, 2H), 7.18 (t, J = 7.6 Hz, 1H), 7.04 (t, J = 8.0 Hz, 2H), 6.22 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 191.6, 144.3, 139.3, 135.0, 134.2, 133.9, 131.9, 131.0, 130.7, 130.2, 129.0, 128.9, 128.8, 128.3. Anal. Calcd for C27H20BrNO5S2: C, 55.67; H, 3.46; N, 2.40%. Found: C, 55.92; H, 3.42; N, 2.32%. (E)-N-(3-(4-Cyanophenyl)-3-oxo-1-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4f). Light yellow solid (81%, 85 mg). Rf = 0.55 (PE:EA = 89:11). mp 175−176 °C. 1H NMR (400 MHz, CDCl3, δ): 7.87−7.84 (m, 6H), 7.64−7.60 (m, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.44 (t, J = 8.0 Hz, 4H), 7.22−7.20 (m, 2H), 7.17− 7.13 (m, 1H), 7.01 (t, J = 8.0 Hz, 2H), 6.23 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 191.8, 146.1, 139.4, 139.2, 134.4, 133.8, 132.3, 130.6, 130.4, 130.2, 129.5, 129.1, 128.9, 128.4, 117.9, 116.3. Anal. Calcd for C28H20N2O5S2: C, 63.62; H, 3.81; N, 5.30%. Found: C, 63.41; H, 3.84; N, 5.39%. (E)-N-(3-(Naphthalen-2-yl)-3-oxo-1-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4g). White solid (90%, 99 mg). Rf = 0.50 (PE:EA = 90:10). mp 153−154 °C. 1H NMR (400 MHz, CDCl3, δ): 8.48 (s, 1H), 7.92−7.87 (m, 6H), 7.77 (t, J = 8.8 Hz, 2H), 7.62−7.42 (m, 8H), 7.35 (d, J = 7.6 Hz, 2H), 7.08 (t, J = 7.6 Hz, 1H), 6.99 (t, J = 8.0 Hz, 2H), 6.39 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 192.4, 143.7, 139.4, 135.7, 134.25, 134.21, 133.5, 132.5, 131.8, 130.1, 129.97, 129.94, 129.0, 128.9, 128.6, 128.2, 127.7, 126.8, 124.0. Anal. Calcd for C31H23NO5S2: C, 67.25; H, 4.19; N, 2.53%. Found: C, 67.07; H, 4.14; N, 2.48%. (E)-N-(3-Oxo-3-phenyl-1-(p-tolyl)prop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4h). White solid (83%, 85 mg). Rf = 0.45 (PE:EA = 89:11). mp 125−126 °C. 1H NMR (400 MHz, CDCl3, δ): 7.89−7.85 (m, 6H), 7.62−7.58 (m, 2H), 7.43 (t, J = 8.4 Hz, 5H), 7.32 (t, J = 7.6 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 6.83 (d, J = 8.0 Hz, 2H), 6.23 (s, 1H), 2.21 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 192.6, 144.1, 140.3, 139.4, 136.3, 134.1, 133.5, 131.2, 130.9, 130.2, 129.3, 129.0, 128.9, 128.7, 21.3. Anal. Calcd for C28H23NO5S2: C, 64.97; H, 4.48; N, 2.71%. Found: C, 65.20; H, 4.41; N, 2.65%. (E)-N-(1-(4-Methoxyphenyl)-3-oxo-3-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4i). Yellow solid (77%, 82

mg). Rf = 0.45 (PE:EA = 92:8). mp 129−130 °C. 1H NMR (400 MHz, CDCl3, δ): 7.90−7.84 (m, 6H), 7.62−7.58 (m, 2H), 7.47−7.41 (m, 5H), 7.31 (t, J = 7.6 Hz, 2H), 7.22−7.20 (m, 2H), 6.55−6.53 (m, 2H), 6.18 (s, 1H), 3.70 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3, δ): 192.7, 161.0, 144.0, 139.5, 136.4, 134.1, 133.4, 132.0, 130.1, 129.3, 129.0, 128.9, 128.6, 126.5, 113.6, 55.4. Anal. Calcd for C28H23NO6S2: C, 63.02; H, 4.34; N, 2.62%. Found: C, 62.85; H, 4.40; N, 2.69%. (E)-N-(1-(3-Fluorophenyl)-3-oxo-3-phenylprop-1-en-1-yl)-N(phenylsulfonyl)benzenesulfonamide (4j). White solid (80%, 83 mg). Rf = 0.40 (PE:EA = 93:7). mp 142−143 °C. 1H NMR (400 MHz, CDCl3, δ): 7.91−7.84 (m, 6H), 7.65−7.61 (m, 2H), 7.47 (t, J = 8.0 Hz, 5H), 7.34 (t, J = 8.0 Hz, 2H), 7.11−7.00 (m, 3H), 6.89−6.84 (m, 1H), 6.31 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 192.1, 162.3 (JC−F = 246.0 Hz), 142.1 (JC−F = 3.0 Hz), 139.2, 136.2 (JC−F = 8.0 Hz), 136.1, 134.4, 133.8, 132.8, 129.8 (JC−F = 8.0 Hz), 129.3, 129.1, 128.9, 128.8, 126.2 (JC−F = 2.0 Hz), 117.0 (JC−F = 6.0 Hz), 116.8 (JC−F = 9.0 Hz). Anal. Calcd for C27H20FNO5S2: C, 62.18; H, 3.87; N, 2.69%. Found: C, 62.01; H, 3.93; N, 2.79%. (E)-3-Amino-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one (5). White solid (73%, 35 mg). Rf = 0.45 (PE:EA = 88:12). mp 75−76 °C. 1H NMR (400 MHz, CDCl3, δ): 10.40 (br s, 1H), 7.97−7.94 (m, 2H), 7.64−7.62 (m, 2H), 7.51−7.45 (m, 3H), 7.12−7.08 (m, 2H), 6.09 (s, 1H), 5.45 (br s, 1H). 13C{1H} NMR (100 MHz, CDCl3, δ): 188.8, 166.0, 163.3 (JC−F = 35 Hz), 137.6, 130.9, 129.6 (JC−F = 9 Hz), 129.2, 128.4, 126.4, 115.3 (JC−F = 27 Hz), 91.6. Anal. Calcd for C15H12FNO: C, 74.68; H, 5.01; N, 5.81%. Found: C, 74.94; H, 4.98; N, 5.89%.

■

ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b01882.

■

Scanned copies of 1H and 13C{1H} NMR spectra of the synthesized compounds (PDF) X-ray crystallographic data for compound 3i (CIF) X-ray crystallographic data for compound 4c (CIF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Sadhanendu Samanta: 0000-0003-2215-9189 Alakananda Hajra: 0000-0001-6141-0343 Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS A.H. acknowledges the financial support from SERB-DST (Grant EMR/2016/001643). S.S. thanks UGC-New Delhi (UGC-SRF) for his fellowship.

■

REFERENCES

(1) (a) Krause, N.; Hashmi, A. S. K. Modern Allene Chemistry; 2004. (b) Ma, S. Some Typical Advances in the Synthetic Applications of Allenes. Chem. Rev. 2005, 105, 2829−2871. (c) Krause, N. Cumulenes and Allenes. Science of Synthesis; Thieme: Stuttgart, Germany, 2007; Vol. 44. (d) Yu, S.; Ma, S. Allenes in Catalytic Asymmetric Synthesis and Natural Product Syntheses. Angew. Chem., Int. Ed. 2012, 51, 3074−3112. (2) (a) Yoshida, M.; Sugimura, C. Synthesis of Tetrasubstituted Pyrroles by Palladium-Catalyzed Cyclization of Propargylic Carbonates with β-Enamino Esters. Tetrahedron Lett. 2013, 54, 2082−2084. (b) Li, Y.; Xu, H.; Xing, M.; Huang, F.; Jia, J.; Gao, J. IodinePromoted Construction of Polysubstituted 2,3-Dihydropyrroles from 13163

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry Chalcones and β-Enamine Ketones (Esters). Org. Lett. 2015, 17, 3690−3693. (3) (a) Hoffmann-Röder, A.; Krause, N. Synthesis and Properties of Allenic Natural Products and Pharmaceuticals. Angew. Chem., Int. Ed. 2004, 43, 1196−1216. (b) Edafiogho, I. O.; Kombian, S. B.; Ananthalakshmi, K. V. V.; Salama, N. N.; Eddington, N. D.; Wilson, T. L.; Alexander, M. S.; Jackson, P. L.; Hanson, C. D.; Scott, K. R. Enaminones: Exploring Additional Therapeutic Activities. J. Pharm. Sci. 2007, 96, 2509−2531. (4) (a) Taylor, D. R. The Chemistry of Allenes. Chem. Rev. 1967, 67, 317−359. (b) Zimmer, R.; Dinesh, C. U.; Nandanan, E.; Khan, F. A. Palladium-Catalyzed Reactions of Allenes. Chem. Rev. 2000, 100, 3067−3125. (5) (a) Wei, L. L.; Xiong, H.; Hsung, R. P. The Emergence of Allenamides in Organic Synthesis. Acc. Chem. Res. 2003, 36, 773−782. (b) Lu, T.; Lu, Z.; Ma, Z.-X.; Zhang, Y.; Hsung, R. P. Allenamides: A Powerful and Versatile Building Block in Organic Synthesis. Chem. Rev. 2013, 113, 4862−4904. (c) Evans, P. A.; Lawler, M. J. RhodiumCatalyzed Propargylic Substitution: A Divergent Approach to Propargylic and Allenyl Sulfonamides. Angew. Chem., Int. Ed. 2006, 45, 4970−4972. (d) Demmer, C. S.; Benoit, E.; Evano, G. Synthesis of Allenamides by Copper-Catalyzed Coupling of Propargylic Bromides and Nitrogen Nucleophiles. Org. Lett. 2016, 18, 1438− 1441. (e) Danowitz, A.; Taylor, C.; Shrikian, T.; Mapp, A. PalladiumCatalyzed [3,3]-Rearrangement for the Facile Synthesis of Allenamides. Org. Lett. 2010, 12, 2574−2577. (6) (a) Hayashi, S.; Phadtare, S.; Zemlicka, J.; Matsukura, M.; Mitsuya, H.; Broder, S. Adenallene and Cytallene : Acyclic Nucleoside Analogues That Inhibit Replication and Cytopathic Effect of Human Immunodeficiency Virus in Vitro. Proc. Natl. Acad. Sci. U. S. A. 1988, 85, 6127. (b) Rivera-Fuentes, P.; Diederich, F. Allenes in Molecular Materials. Angew. Chem., Int. Ed. 2012, 51, 2818−2828. (7) Megati, S.; Goren, Z.; Silverton, J. V.; Orlina, J.; Nishimura, H.; Shirasaki, T.; Mitsuya, H.; Zemlicka, J. (R)-(−)- and (S)(+)-Adenallene: Synthesis, Absolute Configuration, Enantioselectivity of Antiretroviral Effect, and Enzymic Deamination. J. Med. Chem. 1992, 35, 4098−4104. (8) (a) Padwa, A.; Caruso, T.; Nahm, S.; Rodriguez, A. Interconversion of Dipoles by the Flash Vacuum Pyrolysis of Oxadiazolinones. J. Am. Chem. Soc. 1982, 104, 2865−2871. (b) Fenández, I.; Monterde, M. I.; Plumet, J. On the Base-Induced Isomerization of Cyclic Propargylamides to Cyclic Allenamides. Tetrahedron Lett. 2005, 46, 6029−6031. (9) Overman, L. E.; Clizbe, L. A.; Freerks, R. L.; Marlowe, C. K. Thermal Rearrangements of Propargylic Trichloroacetimidates. Synthesis of (Trichloroacetamido)-1,3-Dienes and −1,2-Dienes. J. Am. Chem. Soc. 1981, 103, 2807−2815. (10) (a) Kimura, M.; Wakamiya, Y.; Horino, Y.; Tamaru, Y. Efficient Synthesis of 4-Ethenylidene-2-Oxazolidinones via Palladium-Catalyzed Aminocyclization of 2-Butyn-1,4-Diol Biscarbamates. Tetrahedron Lett. 1997, 38, 3963−3966. (b) Kozawa, Y.; Mori, M. Synthesis of Different Ring-Size Heterocycles from the Same Propargyl Alcohol Derivative by Ligand Effect on Pd(0). Tetrahedron Lett. 2002, 43, 1499−1502. (11) (a) Cao, J.; Kong, Y.; Deng, Y.; Lai, G.; Cui, Y.; Hu, Z.; Wang, G. Synthesis of Allenamides by Pd-Catalyzed Coupling of 3Alkoxycarbonyloxy Ynamides or 1-Alkoxycarbonyloxy Allenamides with Arylboronic Acids. Org. Biomol. Chem. 2012, 10, 9556−9561. (b) Brioche, J.; Meyer, C.; Cossy, J. Synthesis of Functionalized Allenamides from Ynamides by Enolate Claisen Rearrangement. Org. Lett. 2013, 15, 1626−1629. (12) (a) Trost, B. M.; Stiles, D. T. Synthesis of Allenamides by Copper-Catalyzed Coupling of Allenyl Halides with Amides, Carbamates, and Ureas. Org. Lett. 2005, 7, 2117−2120. (b) Shen, L.; Hsung, R. P.; Zhang, Y.; Antoline, J. E.; Zhang, X. CopperCatalyzed Stereospecific N-Allenylations of Amides. Syntheses of Optically Enriched Chiral Allenamides. Org. Lett. 2005, 7, 3081− 3084.

(13) (a) Zhang, G.; Xiong, T.; Wang, Z.; Xu, G.; Wang, X.; Zhang, Q. Highly Regioselective Radical Amination of Allenes: Direct Synthesis of Allenamides and Tetrasubstituted Alkenes. Angew. Chem., Int. Ed. 2015, 54, 12649−12653. (b) Wang, X.; Wu, Z.; Wang, J. α-Fluoroallenoate Synthesis via N-Heterocyclic CarbeneCatalyzed Fluorination Reaction of Alkynals. Org. Lett. 2016, 18, 576−579. (14) Peshkov, V. A.; Pereshivko, O. P.; Nechaev, A. A.; Peshkov, A. A.; Van der Eycken, E. V. Reactions of Secondary Propargylamines with Heteroallenes for the Synthesis of Diverse Heterocycles. Chem. Soc. Rev. 2018, 47, 3861−3898. (15) Li, Y.; Zhang, Q. N-Fluorobenzenesulfonimide: An Efficient Nitrogen Source for C-N Bond Formation. Synthesis 2015, 47, 159− 174. (16) (a) Qiu, S.; Xu, T.; Zhou, J.; Guo, Y.; Liu, G. PalladiumCatalyzed Intermolecular Aminofluorination of Styrenes. J. Am. Chem. Soc. 2010, 132, 2856−2857. (b) Sun, J.; Zheng, G.; Xiong, T.; Zhang, Q.; Zhao, J.; Li, Y.; Zhang, Q. Copper-Catalyzed Hydroxyl-Directed Aminoarylation of Alkynes. ACS Catal. 2016, 6, 3674−3678. (c) Murakami, K.; Perry, G. J. P.; Itami, K. Aromatic C-H Amination: A Radical Approach for Adding New Functions into Biology- and Materials-Oriented Aromatics. Org. Biomol. Chem. 2017, 15, 6071− 6075. (d) Yang, D.; Sun, M.; Wei, W.; Li, J.; Sun, P.; Zhang, Q.; Tian, L.; Wang, H. Copper-Catalyzed Decarboxylative Stereospecific Amidation of Cinnamic Acids with N-fluorobenzenesulfonimide. RSC Adv. 2016, 6, 72361−72365. (e) Rit, R. K.; Shankar, M.; Sahoo, A. K. C-H Imidation: A Distinct Perspective of C-N Bond Formation. Org. Biomol. Chem. 2017, 15, 1282−1293. (17) (a) Nakamura, M.; Endo, K.; Nakamura, E. Indium-Catalyzed Addition of Active Methylene Compounds to 1-Alkynes. J. Am. Chem. Soc. 2003, 125, 13002−13003. (b) Itoh, Y.; Tsuji, H.; Yamagata, K. I.; Endo, K.; Tanaka, I.; Nakamura, M.; Nakamura, E. Efficient Formation of Ring Structures Utilizing Multisite Activation by Indium Catalysis. J. Am. Chem. Soc. 2008, 130, 17161−17167. (c) Ranu, B. C. Indium Metal and Its Halides in Organic Synthesis. Eur. J. Org. Chem. 2000, 2000, 2347−2356. (d) Ranu, B. C.; Jana, U. Indium(III) Chloride-Promoted Rearrangement of Epoxides: A Selective Synthesis of Substituted Benzylic Aldehydes and Ketones. J. Org. Chem. 1998, 63, 8212−8216. (e) Shen, Z.-L.; Wang, S.-Y.; Chok, Y.-K.; Xu, Y.-H.; Loh, T.-P. Organoindium Reagents: The Preparation and Application in Organic Synthesis. Chem. Rev. 2013, 113, 271−401. (f) Kundu, D.; Samim, Md.; Majee, A.; Hajra, A. Indium Triflate-Catalyzed Coupling between Nitroalkenes and Phenol/Naphthols: A Simple and Direct Synthesis of Arenofurans by a Cyclization Reaction. Chem. - Asian J. 2011, 6, 406−409. (18) Lee, D.; Kim, S.-M.; Hirao, H.; Hong, S. H. Gold(I)/Gold(III)Catalyzed Selective Synthesis of N-Sulfonyl Enaminone Isomers from Sulfonamides and Ynones via Two Distinct Reaction Pathways. Org. Lett. 2017, 19, 4734−4737. (19) (a) Monir, K.; Bagdi, A. K.; Ghosh, M.; Hajra, A. Unprecedented Catalytic Activity of Fe(NO3)3·9H2O: Regioselective Synthesis of 2-Nitroimidazopyridines via Oxidative Amination. Org. Lett. 2014, 16, 4630−4633. (b) Mondal, S.; Samanta, S.; Jana, S.; Hajra, A. (Diacetoxy)iodobenzene-Mediated Oxidative C−H Amination of Imidazopyridines at Ambient Temperature. J. Org. Chem. 2017, 82, 4504−4510. (c) Mondal, S.; Samanta, S.; Singsardar, M.; Hajra, A. Aminomethylation of Imidazoheterocycles with Morpholine. Org. Lett. 2017, 19, 3751−3754. (20) (a) Further information can be found in the CIF file. This crystal was deposited in the Cambridge Crystallographic Data Centre and assigned as CCDC 1849791. (b) Further information can be found in the CIF file. This crystal was deposited in the Cambridge Crystallographic Data Centre and assigned as CCDC 1849790. (21) Reddy, C. R.; Prajapti, S. K.; Ranjan, R. Cu(I)-Catalyzed Aminative Aza-Annulation of Enynyl Azide using N-Fluorobenzenesulfonimide: Synthesis of 5-Aminonicotinates. Org. Lett. 2018, 20, 3128−3131. 13164

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165

Article

The Journal of Organic Chemistry (22) Jana, S.; Dey, A.; Singsardar, M.; Bagdi, A. K.; Hajra, A. Zn(OTf)2-Catalyzed Synthesis of Imidazole-Substituted Allenes. J. Org. Chem. 2016, 81, 9489−9493. (23) Albaladejo, M. J.; Alonso, F.; González-Soria, M. J. Synthetic and Mechanistic Studies on the Solvent-Dependent Copper-Catalyzed Formation of Indolizines and Chalcones. ACS Catal. 2015, 5, 3446− 3456.

13165

DOI: 10.1021/acs.joc.8b01882 J. Org. Chem. 2018, 83, 13157−13165