Sulfur Mediated Electrophilic Cyclization of Aryl Substituted Internal

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Sulfur Mediated Electrophilic Cyclization of Aryl Substituted Internal Alkynes Zhong Zhang, Pan He, Hongguang Du, Jiaxi Xu, and Pingfan Li J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b00136 • Publication Date (Web): 08 Mar 2019 Downloaded from http://pubs.acs.org on March 8, 2019

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The Journal of Organic Chemistry

Sulfur Mediated Electrophilic Cyclization of Aryl Substituted Internal Alkynes Zhong Zhang, Pan He, Hongguang Du,* Jiaxi Xu,* and Pingfan Li* State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China. Supporting Information

ABSTRACT: A sulfur mediated electrophilic cyclization reaction of aryl tethered internal alkynes has been developed. Triflic anhydride activated sulfoxides induced the electrophilic cyclization, then demethylation with triethylamine in one-pot, affording 3-sulfenyl-1,2-dihydronaphthalenes and related types of products up to 96% yields.

As an efficient method to synthesize carbocycles and heterocycles, electrophilic cyclization of alkynes have been wildly researched for decades.1 By changing the electrophiles that induce such cyclization, different kinds of functional groups can be introduced to the products in the process of synthesis 3,4-dihydronaphthalene derivatives from 4-arylalkynes. For example, halogen-substituted compounds could be synthesized by using I2, NXS, ICl, IPy2BF4 or other halogen reagents.1a,2 Besides, the boron, selenium, or phosphorous substituted products can be prepared by using boron trichloride,3 diphenyl diselenide4 or Tf2O activated diphenylphosphine oxide,5 respectively. Though several electrophilic sulfenylating reagents such as arylsulfenyl chlorides6 and N-sulfenylsuccinimide7 have been reported, sulfenylating reagent applied in electrophilic cyclization of aryl tethered alkynes to prepare 3-phenylsulfenyl-1,2-dihydronathalene remains rare.8 Recently, Zou and Zhang’s group9 reported Mn(OAc)3 initiated radical reaction of diphenylphosphinoyl and alkynes to prepare 2-phosphinoylated 3,4-dihydronaphthalenes (Scheme 1a). Miura’s group5 got the same product under triflic anhydride activated diphenylphosphine oxide conditions through an electrophilic phosphinative cyclization reaction (Scheme 1b). We reasoned that application of triflic anhydride activated sulfoxide as an electrophilic reagent could induce cyclization reaction to give corresponding sulfur substituted products efficiently. Anhydride activated sulfoxides10 have been widely utilized as the sulfenylating reagents in intermolecular or intramolecular reactions with arenes11 or alkenes,12 but the reaction with alkynes is still rare except for Procter’s work on the synthesis of sulfonium salts as precursors for nickel catalyzed cross-coupling reactions.13 As part of our group’s research on sulfur mediated C-H

Scheme 1. Preparation of 3-substituted-1,2-dihydronaphthalenes from 4-arylalkynes

functionalization reactions,14 we report, herein, the use of triflic anhydride activated sulfoxides as the sulfur electrophiles to active aryl tethered alkynes for intramolecular electrophilic cyclization (Scheme 1c). As strong electrophiles, triflic anhydride activated sulfoxides were envisioned to react with the carboncarbon triple bond to generate vinyl carbon cation intermediates A, which may be captured by the tethered aryl ring to give in-

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termediates B and sulfonium salts C after deprotonation. Demethylation with Et3N (SN2 process) could then afford the desired products. The alkyne 1a and methyl phenyl sulfoxide (2a) were selected as model substrates to optimize the reaction conditions (Table 1). Initially, potassium acetate was used as the base. Gratifyingly, 3-sulfenyl-1,2-dihydronaphthalene (3aa) was obtained in 70% isolated yield (entry 1). Then, different kinds of bases were examined for the demethylation step. When the diethylamine was used as the base, the yield increased to 87% (entry 2). It was found that most of the amine bases could give good yields (entries 2-7). No product was detected when DBU was used as the base because of its poor nucleophilicity (entry 3). Triethylamine showed the best result to afford the desired product 3aa in 94% NMR yield (entry 7). We tried to reduce the loading of base. 96% yield of 3aa was obtained when 4 equivalents of triethylamine were added to the system (entry 8). 40% and 86% yields were obtained when the amount of base was reduced to 2 and 3 equivalents (entries 9-10). Further studies showed that the yield would decreased with shorter reaction time in the demethylation stage (data not shown). In accordance to the supposed SN2 mechanism for the demethylation step, when the methyl group in sulfoxide 2a was changed to ethyl or isopropyl groups, the yield of product 3aa decreased to 13% and 7%, respectively.

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was used. Sulfoxides 2d-h bearing electron-withdrawing groups including halo, formyl, cyano, and nitro groups, all gave the products in good yields (3ad-3ah). Sulfoxides 2i and 2j gave the desired products 3ai and 3aj in 90% and 93% yields. These results show that the electronic and steric effects of sulfoxides have limited impact on the electrophilic cyclization. Besides, dimethyl sulfoxide 2l can also be used in this reaction, and the desired product 3al was afforded in 52% yield. Table 2 Scope of sulfoxides 2a

Table 1 Optimization of reaction conditionsa

Time/h Yield/% b

Entry

base

Equiv (base)

1

KOAc

5

12

70c

2

Et2NH

5

2

87

3

iPr2NH

5

2

83

4

DABCO

5

2

86

5

DMAP

5

2

87

6

DBU

5

2

0

7

Et3N

5

2

94

8

Et3N

4

2

96 (94c)

9

Et3N

3

2

86

10

Et3N

2

2

40

a

Reaction conditions: A solution of 1a (0.4 mmol) and 2a (0.48 mmol) in 2 mL of CH2Cl2 was treated with Tf2O (0.48 mmol) at 78 °C, then warmed up to room temperature, and base was added. b NMR yields. c Isolated yields after column chromatography.

With the optimum reaction conditions in hand, the reactions between alkyne 1a and various aryl methyl sulfoxides 2 were investigated (Table 2). The sulfoxides 2a,k bearing methyl at ortho- and para-positions of aryl groups afforded the products 3ab and 3ak in 96% and 94% yields, respectively. The yield of 3ac decreased to 72% when a methoxy substituted sulfoxide 2c

The electronic and steric effects of alkynes 1 were investigated (Table 3). In general, the aromatic rings of R2 containing both electron-donating and electron-withdrawing groups could give good yields (3aa-3ha). However, the substrate 1h bearing a strong electron-withdrawing group like cyano gave a lower yield of 65% (3ha). Ortho-phenyl substituted substrate 1d gave the product 3da in 83% yield. To our delight, alkyl substituted alkyne 1i afforded the product in 70% yield. Various 4-aryl-1-phenyl-1-butynes were examined in the reaction. The substrates possessing electron-withdrawing groups such as halo and cyano, can smoothly react with activated sulfoxide 2a to afford the corresponding products 3ja-3la in good yields. Methyl substituted alkyne 1m can gave the product 3ma in 81% yield. Alkyne 1n gave a lower 68% yield, probably due to its steric hindrance. Meta-substituted substrate 1o has regioselectivity issue during the cyclization. So both products 3oa and 3oa’ were obtained in 59% and 32% yields, respectively. It is remarkable that 2-(phenylethynyl)-1,1'-biphenyl (1p) gave phenylsulfenyl phenanthrene 3pa in 74% yield. The cyclization of 1q confirms that this methodology is not limited to prepare dihydronaphthalenes, but also dihydroquinoline. The substrates 1r and 1s afforded the corresponding coumarin and 2H-chromene products 3ra and 3sa in 29% and 32% yields, respectively. Many kinds of byproducts were generated in the case of 1s, probably due to the enhancement of aryl ring’s nucleophilicity by the alkoxy substituent. The indene type product


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3ta was afforded in 37% yield, indicating that formation of sixmembered ring products is easier than that of the five-membered ring products. Table 3 Scope of alkynes 1a

benzoic acid as the oxidant in dichloromethane. When 3 equivalents of meta-chloroperbenzoic acid were applied, sulfone 5 was obtained in 91% yield. In conclusion, we have developed a new method to prepare 3-sulfenyl-1,2-dihydronaphthalenes by sequentially introducing triflic anhydride and triethylamine to the mixture of internal alkynes and sulfoxides in one-pot. Various functional groups in alkynes and sulfoxides were tolerated to afford good yields. This method can also be used to synthesize sulfenyl substituted phenanthrene, dihydroquinoline, 2H-chromene, and coumarin in good to moderate yields.

EXPERIMENTAL SECTION General Information. All reactions were carried out in ovendried glassware under a nitrogen atmosphere employing standard techniques unless otherwise noted. Dichloromethane was refluxed over CaH2, and freshly distilled prior to use. Flash column chromatography was performed using silica gel (normal phase, 200-300 mesh). Petroleum ether used for column chromatography were 60-90 oC fraction, and the removal of residue solvent was accomplished under rotovap with repeated azeotrope with chloroform, and then evaporation under vacuum (< 1 mmHg pressure). Reactions were monitored by thin-layer chromatography on silica gel 60-F254 coated 0.2 mm plates. The plates were visualized under UV light. 1H and 13C NMR spectra were recorded on a 400 MHz spectrometer, usually in CDCl3 with TMS as an internal standard, and the chemical shifts (δ) were reported in parts per million (ppm). The IR spectra (KBr pellets, v [cm−1]) were taken on a FTIR spectrometer. HRMS measurements were carried out on a TOF mass spectrometer. Substituted alkynes 1a,3 1b,3 1c,3 1d,15 1e,16 1f,17 1g,5 1h,3 1i,18 1l3, 1m,3 1o,3 1p,15 1q,19 1r,20 1s19 and 1t21 were known and prepared according to published procedures. Alkynes 1j, 1k, and 1n were unknown and were synthesized by Sonogashira coupling. Others were commercially available and used as received.

Scheme 2 Further oxidation of 3aa

Further transformations of 3-sulfenyl-1,2-dihydronaphthalene 3aa were carried out (Scheme 2). Sulfoxide 4 was obtained in 96% yield by using 1.05 equivalents of meta-chloroper-

General procedure for the preparation of aryl alkynes 1j, 1k, and 1n. Et3N (30 mL), PdCl2(PPh3)2 (53 mg, 0.075 mmol), iodobenzene (1.224 g, 6.0 mmol) and CuI (29 mg, 0.15 mmol) were added into a flask. After removal of oxygen of the solution in liquid nitrogen condition, substituted but-3-yn-1-ylbenzene (5.0 mmol) was added to the solution under N2 atmosphere and the resulting solution was stirred at room temperature for 12 h. The reaction mixture was filtered and washed with brine (30 mL × 2), and the filtrate was extracted with diethyl ether (50 mL × 3). The combined organic layer was dried over Na2SO4 and concentrated under vacuum. The resulting crude product was purified by flash column chromatography to give the product. 1-Fluoro-4-(4-phenylbut-3-yn-1-yl)benzene (1j). Petroleum/CH2Cl2 25/1 (v/v); yellow solid (0.516 g, 46%); mp 41-43 o C; 1H NMR (400 MHz, CDCl3) δ 7.42 – 7.32 (m, 2H), 7.32 – 7.17 (m, 5H), 6.99 (t, J = 8.7 Hz, 2H), 2.89 (t, J = 7.3 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 161.6 (d, J = 243.9 Hz), 136.3 (d, J = 3.2 Hz), 131.5, 130.0 (d, J = 7.9 Hz), 128.2, 127.7, 123.7, 115.1 (d, J = 21.2 Hz), 89.1, 81.6, 34.3, 21.8; 19F NMR (376 MHz, CDCl3) δ -117.06 (s, 1F); HRMS (ESI) calcd for C16H14F+ [M+H]+ m/z: 225.1074, found: 225.1078. 4-(4-Phenylbut-3-yn-1-yl)benzonitrile (1k). Petroleum



ether/ethyl acetate 20/1 (v/v); white solid (0.844 g, 73%); mp 74-76 oC; 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 8.2 Hz, 2H), 7.35 – 7.31 (m, 2H), 7.30 – 7.26 (m, 3H), 2.97 (t, J = 7.2 Hz, 2H), 2.73 (t, J = 7.2 Hz, 2H); 13C NMR {1H} (101 MHz, CDCl3) δ 146.1, 132.2, 131.5, 129.4, 128.3, 127.9, 123.4, 119.0, 110.3, 88.2, 82.1, 35.1, 21.0; HRMS (ESI) calcd for C17H14N+ [M+H]+ m/z: 232.1121, found: 232.1126. 1-chloro-2-(4-phenylbut-3-yn-1-yl)benzene (1n). Petroleum/CH2Cl2 25/1 (v/v); yellow oil (0.888 g, 74%); 1H NMR (400 MHz, CDCl3) δ 7.78 – 7.69 (m, 4H), 7.67 – 7.52 (m, 5H), 3.43 (t, J = 7.4 Hz, 2H), 3.11 (t, J = 7.4 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 138.0, 133.9, 131.5, 130.8, 129.5, 128.2, 127.9, 127.6, 126.7, 123.8, 89.0, 81.5, 32.9, 19.7; HRMS (ESI) calcd for C16H14Cl+ [M+H]+ m/z: 241.0779, found: 241.0785. General procedure for electrophilic cyclization of alkynes 1. To a flame-dried Schlenk tube, alkyne 1 (0.4 mmol) and sulfoxide 2 (0.48 mmol) were added, and then dissolved with dichloromethane (2 mL) under nitrogen atmosphere before cooling down to -78 ºC (liquid N2/ethyl acetate bath). Tf2O (81 μL, 0.48 mmol) was added dropwise. After stirring for 0.5 h, the mixture was warmed to room temperature and stirred for another 0.5 h, then added Et3N (162 mg, 1.6 mmol). After stirring for 2 h, the solution was extracted with CH2Cl2 (10 mL×3). The combined organic phase was dried over Na2SO4 and concentrated under reduced pressure. The residue was further purified by flash column chromatography on silica gel and afforded the pure product 3. Phenyl(1-phenyl-3,4-dihydronaphthalen-2-yl)sulfane (3aa).8a Synthesized from 1a (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a yellow solid (118 mg, 94%): Rf = 0.43 (petroleum ether/CH2Cl2 = 5/1); mp 97-99 oC; 1H NMR (400 MHz, CDCl3) δ 7.47 – 7.32 (m, 5H), 7.31 – 7.17 (m, 5H), 7.17 – 7.09 (m, 2H), 7.06 (t, J = 6.7 Hz, 1H), 6.68 (d, J = 7.6 Hz, 1H), 2.90 (t, J = 7.7 Hz, 2H), 2.53 (t, J = 7.7 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 140.4, 139.0, 136.2, 135.3, 135.0, 132.2, 130.9, 130.0, 128.9, 128.3, 127.4, 127.2, 127.0, 126.7, 126.4, 126.2, 29.5, 29.4; IR (KBr) ν (cm−1) 3059, 3020, 2935, 1580, 1477, 1439, 743, 700; HRMS (ESI) calcd for C22H19S+ [M+H]+ m/z: 315.1202, found: 315.1206. (1-Phenyl-3,4-dihydronaphthalen-2-yl)(p-tolyl)sulfane (3ab). Synthesized from 1a (0.4 mmol) and 2b (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a yellow solid (126 mg, 96%): Rf = 0.40 (petroleum ether/CH2Cl2 = 5/1); mp 121-122 oC; 1H NMR (400 MHz, CDCl3) δ 7.48 – 7.40 (m, 2H), 7.40 – 7.33 (m, 1H), 7.32 – 7.20 (m, 4H), 7.17 – 6.99 (m, 5H), 6.67 (d, J = 7.3 Hz, 1H), 2.86 (t, J = 7.6 Hz, 2H), 2.53 – 2.41 (m, 2H), 2.32 (s, 3H); 13C {1H} NMR {1H} (101 MHz, CDCl3) δ 139.1, 137.0, 136.3, 134.9, 133.0, 131.7, 131.3, 130.1, 129.7, 128.3, 127.4, 127.1, 126.8, 126.4, 126.0, 29.4, 29.2, 21.1; IR (KBr) ν (cm−1) 3020, 2932, 1595, 1490, 1442, 808, 767, 700; HRMS (ESI) calcd for C23H21S+ [M+H]+ m/z: 329.1358, found: 329.1364. (4-Methoxyphenyl)(1-phenyl-3,4-dihydronaphthalen-2yl)sulfane (3ac). Synthesized from 1a (0.4 mmol) and 2c (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a yellow oil (99 mg, 72%): Rf = 0.37 (petroleum ether/ethyl acetate = 20/1); 1 H NMR (400 MHz, CDCl3) δ 7.45 (t, J = 7.3 Hz, 2H), 7.40 –

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7.34 (m, 1H), 7.33 – 7.27 (m, 4H), 7.13 – 7.06 (m, 2H), 7.06 – 7.00 (m, 1H), 6.85 – 6.79 (m, 2H), 6.65 (d, J = 7.5 Hz, 1H), 3.78 (s, 3H), 2.86 – 2.78 (m, 2H), 2.46 – 2.37 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 159.3, 139.0, 137.4, 136.4, 134.7, 134.3, 134.1, 130.2, 128.3, 127.3, 127.1, 126.6, 126.3, 125.8, 124.9, 114.5, 55.3, 29.3, 28.7; IR (KBr) ν (cm−1) 3058, 2936, 2832, 1591, 1571, 1491, 1286, 1245, 1172, 827, 700; HRMS (ESI) calcd for C23H21SO+ [M+H]+ m/z: 345.1308, found: 345.1302. (4-Bromophenyl)(1-phenyl-3,4-dihydronaphthalen-2yl)sulfane (3ad). Synthesized from 1a (0.4 mmol) and 2d (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a yellow solid (143 mg, 91%): Rf = 0.34 (petroleum ether/CH2Cl2 = 5/1); mp 129-130 oC; 1H NMR (400 MHz, CDCl3) δ 7.46 – 7.35 (m, 5H), 7.27 – 7.23 (m, 2H), 7.21 (d, J = 8.3 Hz, 2H), 7.17 – 7.11 (m, 2H), 7.09 – 7.03 (m, 1H), 6.68 (d, J = 7.7 Hz, 1H), 2.96 – 2.80 (m, 2H), 2.57 – 2.45 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 141.4, 138.8, 136.0, 135.0, 134.7, 132.2, 132.0, 131.3, 129.9, 128.3, 127.5, 127.2, 126.5, 126.4, 120.7, 29.6, 29.4; IR (KBr) ν (cm−1) 2921, 1596, 1471, 1443, 1008, 813, 767, 700; HRMS (ESI) calcd for C22H18SBr+ [M+H]+ m/z: 393.0307, found: 393.0308. (4-Chlorophenyl)(1-phenyl-3,4-dihydronaphthalen-2yl)sulfane (3ae). Synthesized from 1a (0.4 mmol) and 2e (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a white solid (91 mg, 65%): Rf = 0.34 (petroleum ether/CH2Cl2 = 5/1); mp 98-99 oC; 1H NMR (400 MHz, CDCl3) δ 7.42 (t, J = 7.5 Hz, 2H), 7.39 – 7.33 (m, 1H), 7.31 – 7.18 (m, 6H), 7.17 – 7.10 (m, 2H), 7.09 – 7.01 (m, 1H), 6.67 (d, J = 7.6 Hz, 1H), 2.89 (t, J = 7.8 Hz, 2H), 2.50 (t, J = 7.8 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 141.1, 138.8, 136.0, 134.9, 134.0, 132.8, 132.0, 131.5, 129.9, 129.0, 128.3, 127.5, 127.2, 126.4, 126.3, 29.5, 29.4; IR (KBr) ν (cm−1) 3059, 3021, 1593, 1474, 1441, 1389, 1092, 818, 768, 700; HRMS (ESI) calcd for C22H18SCl+ [M+H]+ m/z: 349.0812, found: 349.0803. 4-((1-Phenyl-3,4-dihydronaphthalen-2-yl)thio)benzaldehyde (3af). Synthesized from 1a (0.4 mmol) and 2f (0.48 mmol). Purification by flash column chromatography (petroleum ether/ethyl acetate 50/1, v/v), to give the product as a yellow solid (113 mg, 82%): Rf = 0.20 (petroleum ether/ethyl acetate = 20/1); mp 121-122 oC; 1H NMR (400 MHz, CDCl3) δ 9.92 (s, 1H), 7.75 (d, J = 8.3 Hz, 2H), 7.45 – 7.33 (m, 5H), 7.24 (dd, J = 5.9, 2.1 Hz, 2H), 7.18 (dd, J = 3.7, 2.0 Hz, 2H), 7.12 – 7.05 (m, 1H), 6.72 (d, J = 7.7 Hz, 1H), 3.03 – 2.95 (m, 2H), 2.68 – 2.60 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 191.1, 145.4, 144.8, 138.6, 135.7, 135.3, 133.9, 130.0, 129.6, 128.9, 128.5, 128.3, 127.8, 127.7, 127.3, 126.9, 126.5, 30.3, 29.4; IR (KBr) ν (cm−1) 3058, 2934, 2830, 1698, 1590, 1562, 1211, 700; HRMS (ESI) calcd for C23H19SO+ [M+H]+ m/z: 343.1151, found: 343.1147. 4-((1-Phenyl-3,4-dihydronaphthalen-2-yl)thio)benzonitrile (3ag). Synthesized from 1a (0.4 mmol) and 2g (0.48 mmol). Purification by flash column chromatography (petroleum ether/ethyl acetate 50/1, v/v), to give the product as a pale yellow solid (120 mg, 88%): Rf = 0.36 (petroleum ether/ethyl acetate = 20/1); mp 168-169 oC; 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.4 Hz, 2H), 7.46 – 7.34 (m, 5H), 7.25 – 7.18 (m, 4H), 7.14 – 7.06 (m, 1H), 6.72 (d, J = 7.7 Hz, 1H), 3.06 – 2.94 (m, 2H), 2.69 – 2.57 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 145.3, 143.8, 138.5, 135.6, 135.2, 132.3, 129.6, 128.7, 128.4,


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128.3, 127.9, 127.7, 127.4, 126.9, 126.6, 118.7, 109.0, 30.3, 29.4; IR (KBr) ν (cm−1) 3074, 3074, 2950, 2218, 1590, 1483, 1449, 1429, 1087, 768; HRMS (ESI) calcd for C23H18NS+ [M+H]+ m/z: 340.1154, found: 340.1148. (4-Nitrophenyl)(1-phenyl-3,4-dihydronaphthalen-2-yl)sulfane (3ah). Synthesized from 1a (0.4 mmol) and 2h (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 5/1, v/v), to give the product as a reddish brown solid (136 mg, 95%): Rf = 0.48 (petroleum ether/ethyl acetate = 20/1); mp 100-101 oC; 1H NMR (400 MHz, CDCl3) δ 8.16 (d, J = 8.9 Hz, 2H), 7.52 – 7.39 (m, 5H), 7.32 – 7.22 (m, 4H), 7.19 – 7.07 (m, 1H), 6.79 (d, J = 7.5 Hz, 1H), 3.07 (t, J = 7.7 Hz, 2H), 2.77 – 2.65 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 146.5, 145.9, 145.5, 138.4, 135.5, 135.2, 129.5, 128.3, 128.0, 127.9, 127.8, 127.4, 127.0, 126.6, 124.0, 30.4, 29.4, IR (KBr) ν (cm−1) 2933, 1578, 1511, 1476, 1338, 851, 742; HRMS (ESI) calcd for C22H18SNO2+ [M+H]+ m/z: 360.1053, found: 360.1059. (3-Nitrophenyl)(1-phenyl-3,4-dihydronaphthalen-2-yl)sulfane (3ai). Synthesized from 1a (0.4 mmol) and 2i (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 5/1, v/v), to give the product as a yellow solid (130 mg, 90%): Rf = 0.45 (petroleum ether/ethyl acetate = 20:1); mp 122-124 oC; 1H NMR (400 MHz, CDCl3) δ 8.16 (t, J = 1.9 Hz, 1H), 8.04 – 7.95 (m, 1H), 7.59 (dd, J = 7.8, 0.5 Hz, 1H), 7.46 – 7.35 (m, 4H), 7.29 – 7.23 (m, 2H), 7.18 (d, J = 4.2 Hz, 2H), 7.12 – 7.04 (m, 1H), 6.71 (d, J = 7.7 Hz, 1H), 3.05 – 2.93 (m, 2H), 2.65 – 2.54 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 148.6, 144.3, 139.2, 138.5, 135.7, 135.2, 135.0, 129.8, 129.6, 129.0, 128.3, 127.8, 127.7, 127.4, 126.8, 126.5, 123.6, 121.0, 30.1, 29.5; IR (KBr) ν (cm−1) 3063, 2935, 1597, 1528, 1481, 1348, 771, 748, 701; HRMS (ESI) calcd for C22H18SNO2+ [M+H]+ m/z: 360.1053, found: 360.1053. (2,4-Dinitrophenyl)(1-phenyl-3,4-dihydronaphthalen-2yl)sulfane (3aj). Synthesized from 1a (0.4 mmol) and 2j (0.48 mmol). Purification by flash column chromatography (petroleum ether/ethyl acetate 20/1, v/v), to give the product as a wine red oil (150 mg, 93%): Rf = 0.27 (petroleum ether/ethyl acetate = 20:1); 1H NMR (400 MHz, CDCl3) δ 9.01 (d, J = 1.8 Hz, 1H), 8.32 (dd, J = 8.9, 2.4 Hz, 1H), 7.79 (d, J = 8.9 Hz, 1H), 7.45 – 7.32 (m, 3H), 7.29 – 7.17 (m, 4H), 7.16 – 7.06 (m, 1H), 6.76 (d, J = 7.7 Hz, 1H), 3.08 (t, J = 7.9 Hz, 2H), 2.72 – 2.61 (m, 2H); 13 C {1H} NMR (101 MHz, CDCl3) δ 150.3, 146.2, 145.2, 144.3, 137.6, 135.4, 135.1, 129.4, 129.1, 128.9, 128.5, 128.1, 127.6, 127.5, 126.8, 126.8, 126.1, 121.8, 30.6, 29.3; IR (KBr) ν (cm−1) 3104, 2937, 1593, 1519, 1443, 1339, 735, 701; HRMS (ESI) calcd for C22H17N2O4S+ [M+H]+ m/z: 405.0904, found: 405.0910. (1-Phenyl-3,4-dihydronaphthalen-2-yl)(o-tolyl)sulfane (3ak). Synthesized from 1a (0.4 mmol) and 2k (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a yellow oil (124 mg, 94%): Rf = 0.40 (petroleum ether/CH2Cl2 = 5/1); 1H NMR (400 MHz, CDCl3) δ 7.48 – 7.33 (m, 4H), 7.32 – 7.26 (m, 2H), 7.18 – 7.07 (m, 5H), 7.07 – 7.00 (m, 1H), 6.66 (d, J = 7.5 Hz, 1H), 2.89 – 2.79 (m, 2H), 2.41 – 2.35 (m, 2H), 2.33 (s, 3H); 13C {1H} NMR (101 MHz, CDCl3) δ 140.1, 139.1, 134.8, 132.8, 132.7, 130.3, 129.9, 128.3, 127.5, 127.4, 127.1, 126.7, 126.4, 126.3, 125.9, 29.2, 29.0, 20.7; IR (KBr) ν (cm−1) 2932, 2832, 1729, 1657, 1604, 1505, 1469, 748, 700; HRMS (ESI) calcd for C23H21S+ [M+H]+ m/z: 329.1358, found: 329.1364.

Methyl(1-phenyl-3,4-dihydronaphthalen-2-yl)sulfane (3al). Synthesized from 1a (0.4 mmol) and 2l (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a white solid (52 mg, 52%): Rf = 0.28 (petroleum ether/CH2Cl2 = 20/1); mp 85-87 oC; 1H NMR (400 MHz, CDCl3) δ 7.46 – 7.39 (m, 2H), 7.38 – 7.31 (m, 1H), 7.24 – 7.18 (m, 2H), 7.13 (d, J = 7.2 Hz, 1H), 7.07 (t, J = 7.3 Hz, 1H), 7.01 (t, J = 7.5 Hz, 1H), 6.57 (d, J = 7.6 Hz, 1H), 2.95 (t, J = 7.8 Hz, 2H), 2.66 (t, J = 7.9 Hz, 2H), 2.22 (s, 3H); 13C {1H} NMR (101 MHz, CDCl3) δ 139.0, 136.3, 134.9, 134.0, 130.1, 128.4, 127.2, 127.0, 126.3, 126.1, 125.0, 28.7, 26.8, 15.1; IR (KBr) ν (cm−1) 3057, 2921, 2829, 1591, 1481, 1440, 765, 700; HRMS (ESI) calcd for C17H17S+ [M+H]+ m/z: 253.1045, found: 253.1053. Phenyl(1-(p-tolyl)-3,4-dihydronaphthalen-2-yl)sulfane (3ba). Synthesized from 1b (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 20/1, v/v), to give the product as yellow oil (107 mg, 81%): Rf = 0.29 (petroleum ether/CH2Cl2 = 5/1); 1H NMR (400 MHz, CDCl3) δ 7.43 – 7.38 (m, 2H), 7.35 – 7.24 (m, 5H), 7.22 (d, J = 8.0 Hz, 2H), 7.20 – 7.15 (m, 2H), 7.13 – 7.08 (m, 1H), 6.76 (d, J = 7.7 Hz, 1H), 2.98 – 2.86 (m, 2H), 2.60 – 2.54 (m, 2H), 2.46 (s, 3H); 13C {1H} NMR (101 MHz, CDCl3) δ 140.3, 137.0, 136.3, 136.0, 135.4, 135.1, 132.0, 130.9, 129.9, 129.0, 128.9, 127.1, 126.9, 126.7, 126.3, 126.3, 29.5, 29.4, 21.4; IR (KBr) ν (cm−1) .2934, 2886, 1582, 1509, 1477, 813, 670; HRMS (ESI) calcd for C23H21S+ [M+H]+ m/z: 329.1358, found: 329.1351. (1-(4-Methoxyphenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3ca). Synthesized from 1c (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a white solid (130 mg, 94%): Rf = 0.55 (petroleum ether/ethyl acetate = 20/1); mp 142-143 oC; 1H NMR (400 MHz, CDCl3) δ 7.38 – 7.33 (m, 2H), 7.27 (t, J = 7.4 Hz, 2H), 7.23 – 7.17 (m, 3H), 7.16 – 7.10 (m, 2H), 7.09 – 7.03 (m, 1H), 6.97 (d, J = 8.6 Hz, 2H), 6.72 (d, J = 7.6 Hz, 1H), 3.85 (s, 3H), 2.93 – 2.80 (m, 2H), 2.56 – 2.46 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 158.8, 139.9, 136.47, 135.4, 135.1, 132.2, 131.2, 131.2, 130.9, 128.9, 127.1, 126.9, 126.7, 126.4, 126.3, 113.7, 55.2, 29.5, 29.4; IR (KBr) ν (cm−1) 2933, 2833, 1609, 1508, 1476, 1439, 1245, 830, 743; HRMS (ESI) calcd for C23H21OS+ [M+H]+ m/z: 345.1308, found: 345.1311. (1-([1,1'-Biphenyl]-2-yl)-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3da). Synthesized from 1d (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 20/1, v/v), to give the product as a yellow oil (129 mg, 83%): Rf = 0.33 (petroleum ether/CH2Cl2 = 5/1); 1 H NMR (400 MHz, CDCl3) δ 7.58 – 7.45 (m, 3H), 7.38 – 7.23 (m, 6H), 7.22 – 7.08 (m, 6H), 6.95 – 6.85 (m, 3H), 2.89 – 2.77 (m, 1H), 2.74 – 2.62 (m, 1H), 2.45 – 2.18 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 141.9, 141.5, 138.4, 137.1, 136.8, 134.8, 132.8, 131.1, 130.2, 129.0, 128.6, 127.9, 127.7, 127.2, 127.1, 126.8, 126.6, 126.6, 126.5, 125.9, 29.1, 28.8; IR (KBr) ν (cm−1) 2930, 2979, 1581, 1476, 1437, 743, 700; HRMS (ESI) calcd for C28H23S+ [M+H]+ m/z: 391.1515, found: 391.1506. (1-(4-Bromophenyl)-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3ea). Synthesized from 1e (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 20/1, v/v), to give the product as a white solid (145 mg, 92%): Rf = 0.35 (petroleum ether/CH2Cl2 = 5/1); mp 144-146 oC; 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 7.7



Hz, 2H), 7.39 (d, J = 7.9 Hz, 2H), 7.33 (t, J = 7.4 Hz, 2H), 7.28 (d, J = 7.4 Hz, 1H), 7.23 – 7.15 (m, 4H), 7.11 (s, 1H), 6.70 (d, J = 7.7 Hz, 1H), 2.93 (t, J = 7.8 Hz, 2H), 2.60 – 2.48 (m, 2H); 13 C {1H} NMR (101 MHz, CDCl3) δ 139.1, 137.9, 135.8, 135.0, 134.8, 132.8, 131.9, 131.5, 131.1, 129.0, 127.3, 127.2, 127.0, 126.5, 126.0, 121.53, 29.5, 29.3; IR (KBr) ν (cm−1) 2939, 2887, 1582, 1481, 1439, 826, 746; HRMS (ESI) calcd for C22H18BrS+ [M+H]+ m/z: 393.0307, found: 393.0306. 1-(4-(2-(Penylthio)-3,4-dihydronaphthalen-1-yl)phenyl)ethan-1-one (3fa). Synthesized from 1f (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/ethyl acetate 10/1, v/v), to give the product as a pale yellow solid (125 mg, 88%): Rf = 0.26 (petroleum ether/ethyl acetate = 5/1); mp 114-115 oC; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.3 Hz, 2H), 7.40 (d, J = 8.2 Hz, 2H), 7.37 – 7.32 (m, 2H), 7.31 – 7.26 (m, 2H), 7.25 – 7.21 (m, 1H), 7.19 – 7.10 (m, 2H), 7.06 (s, 1H), 6.61 (d, J = 7.7 Hz, 1H), 2.93 – 2.87 (m, 2H), 2.64 (s, 3H), 2.57 – 2.50 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 197.8, 144.3, 139.4, 136.1, 135.6, 135.0, 134.7, 132.9, 131.1, 130.5, 129.0, 128.4, 127.4, 127.3, 127.0, 126.5, 125.9, 29.5, 29.3, 26.6; IR (KBr) ν (cm−1) 2934, 2882, 1684, 1598, 1476, 1438, 1266, 832, 741; HRMS (ESI) calcd for C24H21OS+ [M+H]+ m/z: 357.1308, found: 357.1314. Phenyl(1-(4-(trifluoromethyl)phenyl)-3,4-dihydronaphthalen-2-yl)sulfane (3ga). Synthesized from 1g (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a white solid (114 mg, 75%): Rf = 0.34 (petroleum ether/CH2Cl2 = 20/1); mp 87-89 oC; 1H NMR (400 MHz, CDCl3) δ 7.69 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 7.9 Hz, 2H), 7.37 – 7.31 (m, 2H), 7.28 (t, J = 7.4 Hz, 2H), 7.25 – 7.20 (m, 1H), 7.18 – 7.11 (m, 2H), 7.07 (d, J = 5.6 Hz, 1H), 6.59 (d, J = 7.8 Hz, 1H), 2.90 (t, J = 7.8 Hz, 2H), 2.53 (t, J = 7.8 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 142.8, 139.0, 135.6, 135.0, 134.6, 133.2, 131.1, 130.6, 129.53 (q, J = 32.5 Hz), 129.0, 127.4, 127.3, 127.1, 126.5, 125.9, 125.3 (q, J = 3.3 Hz), 124.25 (q, J = 272.5 Hz), 29.51, 29.25; 19F NMR (377 MHz, CDCl3) δ -62.38 (s, 3F); IR (KBr) ν (cm−1) 3063, 2938, 1618, 1581, 1479, 1439, 1325, 1165, 1125, 1066, 838, 742; HRMS (ESI) calcd for C23H18F3S+ [M+H]+ m/z: 383.1076, found: 383.1076. 4-(2-(Phenylthio)-3,4-dihydronaphthalen-1-yl)benzonitrile (3ha). Synthesized from 1h (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 5/1, v/v), to give the product as a pale yellow solid (88 mg, 65%): Rf = 0.40 (petroleum ether/ethyl acetate = 20/1); mp 133-135 oC; 1H NMR (400 MHz, CDCl3) δ 7.73 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.3 Hz, 2H), 7.36 – 7.22 (m, 5H), 7.19 – 7.13 (m, 2H), 7.11 – 7.04 (m, 1H), 6.55 (d, J = 7.6 Hz, 1H), 2.93 – 2.85 (m, 2H), 2.57 – 2.48 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 144.1, 138. 5, 135.3, 135.0, 134.2, 133.7, 132.2, 131.2, 131.1, 129.1, 127.5, 127.3, 126.6, 125.7, 118.9, 111.3, 29.5, 29.2; IR (KBr) ν (cm−1) 2954, 2831, 2227, 1581, 1500, 1476, 1439, 836, 738; HRMS (ESI) calcd for C23H18NS+ [M+H]+ m/z: 340.1154, found: 340.1152. (1-Phenethyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3ia). Synthesized from 1i (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a colorless oil solid (96 mg, 70%): Rf = 0.25 (petroleum ether/CH2Cl2 = 10/1); 1 H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.6 Hz, 1H), 7.32 – 7.10 (m, 15H), 3.26 – 3.15 (m, 2H), 2.90 – 2.82 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.37 (t, J = 7.6 Hz, 2H); 13C {1H} NMR (101

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MHz, CDCl3) δ 141.8, 138.8, 136.2, 135.7, 134.7, 130.8, 130.1, 128.9, 128.5, 128.4, 127.6, 127.0, 126.6, 126.4, 125.9, 123.6, 35.4, 32.1, 29.9, 29.6; IR (KBr) ν (cm−1) 3060, 3024, 2932, 1602, 1582, 1495, 1476, 1452, 1024, 742; HRMS (ESI) calcd for C24H23S+ [M+H]+ m/z: 343.1515, found: 343.1521. (7-Fluoro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3ja). Synthesized from 1j (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 20/1, v/v), to give the product as a yellow oil (108 mg, 94%): Rf = 0.48 (petroleum ether/CH2Cl2 = 5/1); 1H NMR (400 MHz, CDCl3) δ 7.51 (t, J = 7.4 Hz, 2H), 7.47 – 7.39 (m, 3H), 7.38 – 7.27 (m, 5H), 7.16 – 7.07 (m, 1H), 6.85 (td, J = 8.3, 2.0 Hz, 1H), 6.47 (dd, J = 10.4, 1.8 Hz, 1H), 2.89 (t, J = 7.8 Hz, 2H), 2.56 (t, J = 7.8 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 161.6 (d, J = 242.6 Hz), 138.8 (d, J = 2.3 Hz), 138.4, 138.0 (d, J = 7.7 Hz), 134.7, 134.3, 131.5, 130.3 (d, J = 3.0 Hz), 130.0, 129.0, 128.5, 128.1 (d, J = 7.9 Hz), 127.7, 127.1, 113.2 (d, J = 11.6 Hz), 112.9 (d, J = 13.4 Hz), 29.5, 28.6; 19F NMR (376 MHz, CDCl3) δ -116.24 (s, 1F); IR (KBr) ν (cm−1) 2944, 2894, 1605, 1486, 1440, 745, 700; HRMS (ESI) calcd for C22H18FS+ [M+H]+ m/z: 333.1108, found: 333.1116. (7-Isocyano-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3ka). Synthesized from 1k (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 5/1, v/v), to give the product as a white solid (115 mg, 85%): Rf = 0.30 (petroleum ether/ethyl acetate = 20:1); mp 125-126 oC; 1H NMR (400 MHz, CDCl3) δ 7.53 (t, J = 7.3 Hz, 2H), 7.49 – 7.44 (m, 1H), 7.42 (d, J = 7.6 Hz, 3H), 7.38 – 7.28 (m, 5H), 7.25 (d, J = 7.7 Hz, 1H), 6.97 (s, 1H), 2.96 (t, J = 7.8 Hz, 2H), 2.54 (t, J = 7.8 Hz, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 140.0, 137.5, 137.3, 136.8, 136.0, 133.8, 132.1, 130.1, 129.9, 129.0, 128.9, 128.8, 128.0, 127.9, 127.5, 119.1, 110.3, 29.3, 28.5; IR (KBr) ν (cm−1) 2954, 2834, 2227, 1581, 1556, 1476, 1441, 833, 746; HRMS (ESI) calcd for C23H18SN+ [M+H]+ m/z: 340.1154, found: 340.1152. (7-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3la). Synthesized from 1l (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a pale yellow solid (99 mg, 71%): Rf = 0.35 (petroleum ether/CH2Cl2 = 5:1); mp 105-106 oC; 1H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 7.5 Hz, 2H), 7.34 (d, J = 0.9 Hz, 3H), 7.32 – 7.22 (m, 5H), 7.10 – 7.02 (m, 2H), 6.64 (d, J = 1.4 Hz, 1H), 2.87 – 2.80 (m, 2H), 2.51 – 2.44 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 138.4, 138.2, 137.8, 134.6, 134.5, 133.2, 132.1, 131.6, 130.0, 129.0, 128.5, 128.3, 127.7, 127.2, 126.6, 125.9, 29.2, 28.7; IR (KBr) ν (cm−1) 2942, 2822, 1583, 1476, 1439; HRMS (ESI) calcd for C22H18SCl+ [M+H]+ m/z: 349.0812, found: 349.0813. (7-Methyl-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3ma). Synthesized from 1m (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a pale yellow solid (107 mg, 81%): Rf = 0.36 (petroleum ether/CH2Cl2 = 5/1); mp 115-116 oC; 1H NMR (400 MHz, CDCl3) δ 7.46 – 7.30 (m, 5H), 7.25 (dd, J = 10.3, 4.5 Hz, 4H), 7.21 – 7.15 (m, 1H), 7.02 (d, J = 7.5 Hz, 1H), 6.93 (d, J = 7.5 Hz, 1H), 6.47 (s, 1H), 2.87 – 2.79 (m, 2H), 2.53 – 2.46 (m, 2H), 2.15 (s, 3H); 13C {1H} NMR (101 MHz, CDCl3) δ 140.5, 139.1, 136.1, 135.9, 135.4, 132.2, 132.1, 130.9, 130.1, 128.9, 128.3, 127.6, 127.4, 127.1, 126.9, 126.7, 29.7, 29.0, 21.2; IR (KBr) ν (cm−1) 3020, 2929, 1581, 1491, 1475, 1440, 745, 700; HRMS (ESI) calcd for C23H21S+ [M+H]+ m/z: 329.1358, found: 329.1353.


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(5-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3na). Synthesized from 1n (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product as a pale yellow solid (95 mg, 68%): Rf = 0.41 (petroleum ether/CH2Cl2 = 5/1); mp 78-79 oC; 1H NMR (400 MHz, CDCl3) δ 7.44 (t, J = 7.4 Hz, 1H), 7.41 – 7.33 (m, 1H), 7.33 – 7.22 (m, 3H), 7.20 – 7.15 (m, 1H), 6.97 (t, J = 7.9 Hz, 1H), 6.57 (d, J = 7.8 Hz, 1H), 3.05 – 2.98 (m, 1H), 2.54 – 2.48 (m, 1H); 13C {1H} NMR (101 MHz, CDCl3) δ 138.7, 138.1, 134.5, 133.8, 132.8, 132.5, 132.3, 131.5, 130.1, 129.0, 128.4, 127.7, 127.6, 127.2, 126.9, 124.8, 28.6, 25.7; IR (KBr) ν (cm−1) 3057, 2960, 1582, 1552, 1475, 1440, 744, 702; HRMS (ESI) calcd for C22H18SCl+ [M+H]+ m/z: 349.0812, found: 349.0807. (6-Chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3oa) and (8-chloro-1-phenyl-3,4-dihydronaphthalen-2-yl)(phenyl)sulfane (3oa’) Synthesized from 1o (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 25/1, v/v), to give the product 3oa as a pale yellow solid (82 mg, 59%): Rf = 0.39 (petroleum ether/CH2Cl2 = 5/1); mp 112-113 oC; 1H NMR (400 MHz, CDCl3) δ 7.47 – 7.41 (m, 2H), 7.41 – 7.32 (m, 3H), 7.32 – 7.19 (m, 5H), 7.12 (d, J = 1.9 Hz, 1H), 7.01 (dd, J = 8.3, 2.1 Hz, 1H), 6.59 (d, J = 8.3 Hz, 1H), 2.90 – 2.80 (m, 2H), 2.54 – 2.45 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 139.0, 138.5, 136.8, 134.8, 134.8, 132.9, 132.4, 131.3, 130.0, 129.0, 128.4, 127.6, 127.4, 127.2, 127.0, 126.3, 29.2, 29.2; IR (KBr) ν (cm−1) 2940, 2888, 1588, 1476, 1439, 874, 745, 700; HRMS (ESI) calcd for C22H18SCl+ [M+H]+ m/z: 349.0812, found: 349.0806; and 3oa’ as a yellow oil (45 mg, 32%): Rf = 0.34 (petroleum ether/CH2Cl2 = 5/1); 1H NMR (400 MHz, CDCl3) δ 7.40 – 7.32 (m, 4H), 7.32 – 7.21 (m, 6H), 7.11 (d, J = 1.8 Hz, 1H), 7.05 (dd, J = 7.1, 4.6 Hz, 2H), 2.80 – 2.73 (m, 2H), 2.43 – 2.35 (m, 2H); 13 C {1H} NMR (101 MHz, CDCl3) δ 140.3, 140.1, 137.1, 136.7, 134.7, 134.1, 132.2, 131.8, 130.2, 123.0, 129.0, 127.6, 127.2, 127.0, 125.5, 31.0, 29.4; IR (KBr) ν (cm−1) 2921, 2901, 1580, 1489, 1440, 1068, 743, 698; HRMS (ESI) calcd for C22H18SCl+ [M+H]+ m/z: 349.0812, found: 349.0818. Phenyl(10-phenylphenanthren-9-yl)sulfane (3pa).22 Synthesized from 1p (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a yellow solid (107 mg, 74%): Rf = 0.17 (petroleum ether/CH2Cl2 = 10/1); mp 125-127 oC; 1H NMR (400 MHz, CDCl3) δ 8.81 (dd, J = 8.2, 3.5 Hz, 2H), 8.71 – 8.62 (m, 1H), 7.76 – 7.67 (m, 2H), 7.65 – 7.58 (m, 1H), 7.55 – 7.50 (m, 2H), 7.47 – 7.41 (m, 3H), 7.32 – 7.27 (m, 2H), 7.14 – 7.07 (m, 2H), 7.05 – 6.99 (m, 1H), 6.99 – 6.91 (m, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 146.8, 140.2, 139.0, 132.2, 132.1, 131.1, 130.9, 129.5, 128.7, 128.6, 128.04, 127.95, 127.62, 127.59, 127.4, 127.11, 127.06, 126.7, 126.4, 124.7, 122.8, 122.6; IR (KBr) ν (cm−1) 3057, 3024, 1581, 1477, 1440, 1024, 759; HRMS (ESI) calcd for C26H19S+ [M+H]+ m/z: 363.1202, found: 363.1207. 4-Phenyl-3-(phenylthio)-1-tosyl-1,2-dihydroquinoline (3qa). Synthesized from 1q (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/ethyl acetate 30/1, v/v), to give the product as a yellow oil (156 mg, 83%): Rf = 0.25 (petroleum ether/ethyl acetate = 20/1); 1H NMR (400 MHz, CDCl3) δ 7.77 (dd, J = 8.0, 0.8 Hz, 1H), 7.41 – 7.24 (m, 11H), 7.18 (d, J = 8.0 Hz, 2H), 7.08 (td, J = 7.8, 1.0 Hz, 1H), 6.61 (dd, J = 7.9, 1.0 Hz, 1H), 6.58 (dd, J = 6.4, 2.9 Hz, 2H), 4.43 (s, 2H), 2.42 (s, 3H); 13C {1H} NMR (101 MHz, CDCl3) δ

143.7, 136. 7, 136.4, 135.7, 133.8, 132.5, 131.9, 131.4, 129.5, 129.3, 129.2, 128.2, 128.2, 127.7, 127.5, 127.0, 126. 7, 126.2, 126.0, 49.3, 21.4; IR (KBr) ν (cm−1) 2921, 1740, 1664, 1597, 1493, 1476, 1166, 749, 699; HRMS (ESI) calcd for C28H24NO2S2+ [M+H]+ m/z: 470.1243, found: 470.1246. 4-Phenyl-3-(phenylthio)-2H-chromen-2-one (3ra).23 Synthesized from 1r (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/ethyl acetate 20/1, v/v), to give the product as a yellow solid (38 mg, 29%): Rf = 0.18 (petroleum ether/ ethyl acetate = 20/1); mp 150-152 o C; 1H NMR (400 MHz, CDCl3) δ 7.56 – 7.46 (m, 4H), 7.39 (d, J = 8.2 Hz, 1H), 7.27 – 7.23 (m, 2H), 7.22 – 7.12 (m, 6H), 7.12 – 7.08 (m, 1H); 13C {1H} NMR (101 MHz, CDCl3) δ 159.2, 158.9, 153.3, 134.9, 134.8, 132.2, 129.3, 129.0, 128.9, 128.5, 128.3, 128.1, 126.7, 124.3, 121.8, 120.5, 116.8, IR (KBr) ν (cm−1) 3058, 1724, 1603, 1591, 1541, 1478, 994, 756; HRMS (ESI) calcd for C21H15O2S+ [M+H]+ m/z: 331.0787, found: 331.0795. 4-Phenyl-3-(phenylthio)-2H-chromene (3sa). Synthesized from 1s (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a colorless oil (41 mg, 32%): Rf = 0.51 (petroleum ether/CH2Cl2 = 2/1); 1H NMR (400 MHz, CDCl3) δ 7.46 – 7.32 (m, 5H), 7.31 – 7.18 (m, 5H), 7.14 (t, J = 7.7 Hz, 1H), 6.88 (d, J = 8.0 Hz, 1H), 6.82 (t, J = 7.5 Hz, 1H), 6.74 (d, J = 7.7 Hz, 1H), 4.72 (s, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 153.8, 139.2, 136.2, 133.7, 130.1, 129.9, 129.3, 129.2, 128.3, 128.0, 127.0, 126.5, 125.0, 123.3, 121.6, 115.9, 68.32; IR (KBr) ν (cm−1) 3058, 1675, 1598, 1581, 1480, 1452, 1442, 1226, 1040, 747; HRMS (ESI) calcd for C21H17SO+ [M+H]+ m/z: 317.0995, found: 317.0999. Phenyl(3-phenyl-1H-inden-2-yl)sulfane (3ta). Synthesized from 1t (0.4 mmol) and 2a (0.48 mmol). Purification by flash column chromatography (petroleum ether/CH2Cl2 10/1, v/v), to give the product as a colorless oil (44 mg, 37%): Rf = 0.17 (petroleum ether/CH2Cl2 = 10/1); 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 7.9 Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.42 – 7.22 (m, 9H), 7.18 (t, J = 7.3 Hz, 1H), 3.51 (s, 2H); 13C {1H} NMR (101 MHz, CDCl3) δ 144.9, 144.2, 142.9, 135.7, 135.0, 134.2, 131.5, 129.08, 129.06, 128.4, 127.9, 127.2, 126.5, 125.0, 123.5, 119.9, 42.3; IR (KBr) ν (cm−1) 3059, 3024, 1601, 1581, 1476, 1455, 1440, 771; HRMS (ESI) calcd for C21H17S+ [M+H]+ m/z: 301.1045, found: 301.1040. 4-Phenyl-3-(phenylsulfinyl)-1,2-dihydronaphthalene (4). 3aa (1 mmol, 314 mg) was dissolved in CH2Cl2 (5 mL) at 0 oC. A solution of m-CPBA (1.05 mmol, 213 mg, 85%) in CH2Cl2 was added dropwise to the cooled solution. The mixture was stirred for 0.5 h at 0 oC and then stirred at room temperature for another 2 h. Then the mixture was washed with saturated Na2CO3 aqueous solution. The organic layer was dried over Na2SO4 and filtered. Solvent was removed under reduced pressure to give 4 as a white solid (320 mg, 96%); Rf = 0.30 (petroleum ether/ethyl acetate = 5/1); mp 149-151oC; 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 6.9 Hz, 2H), 7.53 – 7.27 (m, 8H), 7.22 (t, J = 7.3 Hz, 1H), 7.15 (d, J = 7.1 Hz, 1H), 7.10 (t, J = 7.5 Hz, 1H), 6.81 (d, J = 7.7 Hz, 1H), 3.05 – 2.92 (m, 1H), 2.92 – 2.71 (m, 2H), 2.21 – 2.07 (m, 1H); 13C {1H} NMR (101 MHz, CDCl3) δ 144.6, 143.1, 141.0, 136.4, 136.0, 134.5, 130.3, 129.3, 128.9, 128.3, 127.9, 127.6, 126.6, 124.6, 28.5, 18.1; IR (KBr) ν (cm−1) 2972, 2831, 1727, 1664, 1606, 1578, 1039, 771; HRMS (ESI) calcd for C22H19OS+ [M+H]+ m/z: 331.1151, found: 331.1154.



4-Phenyl-3-(phenylsulfonyl)-1,2-dihydronaphthalene (5). 3aa (0.2 mmol, 63 mg) was dissolved in CH2Cl2 (2 mL) at 0 oC. A solution of m-CPBA (0.6 mmol, 122 mg, 85%) in CH2Cl2 was added dropwise to the cooled solution. The mixture was stirred for 0.5 h at 0 oC and then stirred at room temperature for another 2 h. Then the mixture was washed with saturated Na 2SO3 and Na2CO3 aqueous solution. The organic layer was dried over Na2SO4 and filtered. Solvent was removed under reduced pressure to give 5 as a white solid (63 mg, 91%); Rf = 0.35 (petroleum ether/ethyl acetate = 50/1); mp 162-164 oC; 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 7.8 Hz, 2H), 7.48 (t, J = 7.4 Hz, 1H), 7.34 (t, J = 7.3 Hz, 3H), 7.31 – 7.20 (m, 3H), 7.17 (d, J = 7.1 Hz, 1H), 7.06 – 6.97 (m, 3H), 6.63 (d, J = 7.9 Hz, 1H), 2.96 (s, 4H); 13C {1H} NMR (101 MHz, CDCl3) δ 146.5, 141.8, 136.7, 136.3, 135.5, 135.0, 132.6, 129.8, 129.7, 128.6, 128.4, 127.7, 127.7, 127.4, 126.7, 28.2, 24.1; IR (KBr) ν (cm−1) 3061, 2926, 1595, 1564, 1489, 1305, 1148, 1087, 776; HRMS (ESI) calcd for C22H19O2S+ [M+H]+ m/z: 347.1100, found: 347.1103.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Copies of 1H NMR, 13C NMR, and 19F NMR spectra for all isolated compounds (PDF)

AUTHOR INFORMATION Corresponding Author * Email: [email protected]. * Email: [email protected]. * Email: [email protected].

ORCID Hongguang Du: 0000-0003-3237-4261; Jiaxi Xu: 0000-0002-9039-4933; Pingfan Li: 0000-0002-0056-9243.

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21402005 and 21572017) and the Fundamental Research Funds for the Central Universities (XK-1802-6).

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