Palladium-Catalyzed Carbene Migratory Insertion and Trapping with

a School of Basic Medical Sciences, Xinxiang Medical University, Xinxiang, Henan, ... b State Key Laboratory of Applied Organic Chemistry, Lanzhou Uni...
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Article Cite This: J. Org. Chem. 2018, 83, 4762−4768

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Palladium-Catalyzed Carbene Migratory Insertion and Trapping with Sulfinic Acid Salts toward Allylic Sulfones Ping-Xin Zhou,*,† Yalei Zhang,† Chunbo Ge,† Yong-Min Liang,*,‡ and Changzheng Li*,† †

School of Basic Medical Sciences, Xinxiang Medical University, Xinxiang, Henan, 453003, China State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, China

‡

S Supporting Information *

ABSTRACT: Allylic sulfones were synthesized with excellent selectivity and good yield via Pd-catalyzed cross-coupling of vinyl iodide with N-tosylhydrazone. This process involves palladium carbene migratory insertion/trapping with sulfinic acid salts. For the previous Pd-catalyzed N-tosylhydrazone crosscoupling, sulfinic acid salt is generated as a byproduct. In this transformation, the diazo compound and the sulfinic acid salt, which are all generated from N-tosylhydrazone, were used as cross-coupling partner.

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INTRODUCTION Due to the activation of the α-carbon, allylic sulfones are essential synthetic precursors in a number of carbon−carbon bond-forming reactions, such as Ramberg-Bäcklund reaction, Michael addition reaction, and Julia olefination.1 Additionally, allylic sulfones are unit constituents of some biologically important compound and pharmaceuticals, such as anticancer agents, weed control herbicides, drugs used in the cure of Alzheimer’s disease, and abnormal cell proliferation diseases.2 Because of their important applications in chemistry and biology, substantial attention has been paid to the development of synthetic methods toward this type of compounds.3 However, the current methods in use have notable drawbacks such as the use of external oxidants, relatively harsh reaction conditions, or preinstallation of a leaving group. Thus, the development of a mild and efficient approach to allylic sulfones remains a topic of great interest. Palladium-catalyzed carbene insertion reactions have been well-established as an indispensable tool for the formation of C−C bonds.4 In the early studies, diazo compounds are widely utilized as a precursor for the generation of palladium carbene species. Over the past years, N-tosylhydrazones have emerged as safe and convenient diazo precursors via in situ generation of unstable diazo species with 1 equiv of sulfinic acid salt released as byproduct. A general mechanism of these transformations involves Pd-carbene complex formation II and subsequent migration insertion of carbene into the Pd−C bond to afford the Csp3-Pd intermediate III.4 The palladium complex III can proceed through a number of subsequent processes, depending on its structure. When there is hydrogen adjacent to the carbene center, the palladium complex III may undergo the β-hydride elimination to afford the alkenes (Scheme 1a).4,5 When the palladium intermediate III does not have a β-hydrogen, the palladium species III can be engaged in different types of cascade processes (Scheme 1b). All of the cascade processes take advantage of the inherent reactivity of the Csp3-Pd intermediate III, involving the η3-benzylpalladium, η3-oxoallylpalladium, and η3-allylpalladium. For example, Wang, Valdés, and Van Vranken have reported that the η3-benzylpalladium intermediate can be © 2018 American Chemical Society

Scheme 1. Mechanisms of Palladium-Catalyzed Reactions of Diazo Compound

trapped by a nucleophile or it can undergo transmetalation with an organometallic reagent or it can react with a double bond.6 Wang, we, and Sekar have reported interception of the η3-oxoallylpalladium intermediate with a double bond for the construction of cyclic architectures or it can also be trapped by a nucleophile.7 We reported that the Pd-catalyzed insertion of an α,β-unsaturated diazo compound could access the η3-allylpalladium intermediates that would then be attacked by amines, enolates, and sulfinic acid salt.7b,8 Van Vranken, Wang, and we have explored the Pd-catalyzed reactions of vinyl halides with N-tosylhydrazone to generate η3-allylpalladium species, which can be trapped by amines, oxygen or enolates (Scheme 2a−c).9 However, in the Pd-catalyzed cross-coupling reaction of vinyl halides with N-tosylhydrazone, sulfinic acid salt was generated as a byproduct. Considering the sulfinic acid salt is also a potential nucleophile in the Pd-catalyzed cross-coupling reactions,10 and continuing with our interest in the Pd-carbene migratory insertion cascade reaction, 7b,8,9b,11 we speculated that η3-allylpalladium intermediates derived from vinyl group migratory insertion into carbene could also be attacked by sulfinic acid salt to generate allylic sulfones (Scheme 2d).

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RESULTS AND DISCUSSION Initially, the reaction was explored by examining the coupling of vinyl iodide 1a with N-tosylhydrazone 2a in toluene at 70 °C Received: March 7, 2018 Published: April 5, 2018 4762

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768

Article

The Journal of Organic Chemistry Scheme 2. Cascade Reactions Involved η3-Allylpalladium Intermediates and This Work

carried out with BTAC as an additive (entry 7). This is maybe due to the fact that the BTAC increases the solubility of the N-tosylhydrazone anion and sulfinate salt in toluene. The yield was further increased to 75% by performing the reaction with dioxane as solvent (entry 9). The effect of catalyst was subsequently examined and revealed that Pd(CH3CN)2Cl2, Pd2(dba)3, and PdCl2 were less efficient catalysts for this transformation (entries 11−13). When the reaction time was decreased to 20 min at 30 °C, a lower yield was observed (entry 14). Finally, control experiment showed that no desired product could be afforded without the palladium catalyst (entry 15). With the optimized conditions in hand, we studied the scope of this reaction. A set of substituted N-tosylhydrazones 2 were coupled to vinyl iodide 1a to form the products 3 (Table 2). N-Tosylhydrazones bearing an electron-donating group delivered 3-2, 3-3, and 3−4 in moderate yield. However, no product or a lower yield of product was observed when N-tosylhydrazones were substituted with electron-withdrawing groups. For the palladium-catalyzed three-component coupling of vinyl halides, diazo compound, and nucleophiles, as demonstrated by Van Vranken’s group and our group, excess nucleophiles need to be used to improve the yield.9a,b,d Encouraged by these previous results, 2.0 equiv of extra TsNa was used. As anticipated, the product was isolated in good to excellent yield and different electron-withdrawing groups, such as CF3 (3-5), fluoro (3-6), chloro (3-7), and bromo (3-8), were all tolerated. Substituents at the ortho-position of the aryl ring are also tolerated, as shown in the formation of 3-14, 3-15, 3-16, and 3-17 in good yield. Finally, furanyl-substituted N-tosylhydrazone was also participated in the coupling, albeit providing the product 3-20 with 42% yield. To probe the reaction scope further, we then studied the scope of this reaction by using various R groups (Table 3). Electrondonating (−OMe) or electron-withdrawing groups (−F and −Cl) on the aryl ring (R = aryl) all proceeded efficiently to lead to the corresponding products 3-24, 3-25, and 3-27 in moderate to good yields. It is noteworthy that steric effect had no significant effect on the reaction, where a substrate with an ortho-methyl group furnished 3-28 in 67% yield. The thiophene containing hydrazone (R = thienyl) was also identified as a suitable substrate for the coupling, delivering the product 3-30 in 57% yield. Furthermore, we are delighted to find that vinyl iodide 1b is a suitable substrate for the cross-coupling with N-tosylhydrazone 2a without addition of TsNa, constructing of a quaternary carbon center in 71% yield (Scheme 3). A plausible catalytic cycle is proposed as shown in Scheme 4. The reaction involves the oxidative addition of Pd(0) to 1 to afford a vinylpalladium iodide complex A. Meanwhile, the diazo compound B and TsK are generated in situ from N-tosylhydrazone 2 in the presence of K2CO3. The palladium species A can react with the diazo compound B to give the palladium-carbene C, followed by migratory insertion to generate η1-allylpalladium intermediate D. The η1-allylpalladium complex could generate η3-allylpalladium intermediate E, which could be trapped by sulfinic acid salt and give 3 as the only product. The selectivity is consistent with previous reports.9

with Pd(OAc)2/PPh3 as catalyst in the presence of Na2CO3 (Table 1, entry 1). To our disappointment, no allylic sulfone Table 1. Optimization of Reaction Conditions for PalladiumCatalyzed Cross-Coupling of Vinyl Iodide 1a with N-Tosylhydrazone 2aa

entry

catalyst

base

slovent

yield (%)

1 2 3 4 5 6 7b 8b 9b 10b 11b 12b 13b 14b,c 15b

Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(OAc)2/PPh3 Pd(CH3CN)2Cl2/PPh3 Pd2(dba)3/PPh3 PdCl2/PPh3 Pd(OAc)2/PPh3

Na2CO3 K2CO3 Cs2CO3 t-BuOLi t-BuONa t-BuOK K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3

toluene toluene toluene toluene toluene toluene toluene THF dioxane CH3CN dioxane dioxane dioxane dioxane dioxane

nr nr nr nr nr nr 48 61 75 7 22 58 33 67 0

a

Reaction conditions are as follows: 1a (0.2 mmol, 1.0 equiv), 2a (0.45 mmol, 2.25 equiv), Pd (10 mol %), ligand (30 mol %), base (0.6 mmol, 3.0 equiv), solvent (2 mL), Ar, at 30 °C for 45 min then 70 °C for 12 h. Yield of the isolated product. bBTAC (benzyl triethylammonium chloride) (0.2 mmol, 1.0 equiv) was used. c Reaction is stirred at 30 °C for 20 min, then 70 °C for 12 h.

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product was obtained under such conditions. Then, an array of different catalytic conditions such as base, Pd sources, and solvent were screened. Switching the base to K2CO3, Cs2CO3, t-BuOLi, t-BuONa, and t-BuOK was not effective (entries 2−6). In previous Pd-catalyzed cross-coupling reactions of sulfinate salt10 and Pd-catalyzed cross-coupling reactions of N-tosylhydrazones,9a,d a phase-transfer catalyst was used as an additive to increase the yield. We were delighted to find that 48% yield of the desired product 3-1 could be afforded when the reaction was

CONCLUSIONS In conclusion, we have developed a novel Pd-catalyzed carbene migratory insertion/nucleophilic addition strategy to access allylic sulfones with excellent selectivity. For the previous Pd-catalyzed N-tosylhydrazone cross-coupling, sulfinic acid salt is a byproduct. In this cross-coupling, sulfinic acid salt, generated from N-tosylhydrazone, is also employed as a nucleophile. 4763

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768

Article

The Journal of Organic Chemistry Table 2. Scope of the Reaction with N-Tosylhydrazones 2a

a

Reaction conditions: 1a (0.2 mmol, 1.0 equiv), 2 (0.45 mmol, 2.25 equiv), Pd(OAc)2 (10 mol %), PPh3 (30 mol %), K2CO3 (0.6 mmol, 3.0 equiv), BTAC (0.2 mmol, 1.0 equiv), dioxane (2 mL), Ar, at 30 °C for 45 min then 70 °C for 12 h. Yield is of the isolated product. bThis reaction was carried out with addition of 2.0 equiv of TsNa. cNMR yield.

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N-tosylhydrazones 214 were synthesized according to the literature procedure. General Procedure for the Preparation of the Products 3. An oven-dried Schlenk tube under a nitrogen atmosphere was charged with vinyl iodide 1 (0.2 mmol, 1.0 equiv), N-tosylhydrazone 2 (0.445 mmol, 2.25 equiv), (if necessary, 2.0 equiv of sulfinic acid salts was added), Pd(OAc)2 (10 mol %), PPh3 (30 mol %), K2CO3 (0.6 mmol, 3.0 equiv), BTAC (0.2 mmol, 1.0 equiv), and dioxane (2 mL). The mixture was stirred at room temperature for 45 min and then stirred at 70 °C for 12 h. The resulting mixture was cooled to room temperature and filtered

EXPERIMENTAL SECTION

General Remarks. The desired product was purified by flash column chromatography, silica gel (200−300 mesh). 1H NMR spectra and 13C NMR spectra were recorded on 400 MHz in CDCl3 and TMS as internal standard. All products were further characterized by HRMS (high resolution mass spectra). Copies of their1 H NMR and 13C NMR spectra are provided. THF, toluene, and 1,4-dioxane were dried over sodium with a benzophenone-ketyl intermediate as indicator. DCE and MeCN were distilled over P2O5. Commercially available reagents and solvents were used without further purification. 1a,12 1b,13 and 4764

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768

Article

The Journal of Organic Chemistry Table 3. Scope of the Reaction with N-Tosylhydrazones 2a

(E)-(3-Tosylpent-1-ene-1,5-diyl)dibenzene (3-1). Yellow solid (56.4 mg, 75%), mp: 110−113 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.66(d, J = 8.0 Hz, 2H), 7.34−7.24(m, 9H), 7.21−7.19(m, 1H), 7.12(d, J = 7.2 Hz, 2H), 6.29(d, J = 16.0 Hz, 1H), 5.94(dd, J = 9.6 Hz, 16.0 Hz, 1H), 3.65−3.59(m, 1H), 2.84−2.77(m, 1H), 2.62−2.50(m, 2H), 2.40(s, 3H), 2.11−2.01(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.5, 140.0, 138.4, 135.8, 134.4, 129.4, 129.1, 128.6, 128.5, 128.4, 126.6, 126.3, 121.0, 68.6, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H24O2SNa: 399.1395; found: 399.1391. (E)-1-Methyl-4-((5-phenyl-1-(p-tolyl)pent-1-en-3-yl)sulfonyl)benzene (3-2). Yellow oil (48.4 mg, 62%); PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.0 Hz, 2H), 7.28−7.24(m, 4H), 7.20−7.18(m, 3H), 7.14−7.11(m, 4H), 6.24(d, J = 16.0 Hz, 1H), 5.91− 5.85(m, 1H), 3.63−3.57(m, 1H), 2.83−2.77(m, 1H), 2.61−2.51 (m, 2H), 2.40(s, 3H), 2.34(s, 3H), 2.08−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ:144.5, 140.0, 138.4, 138.3, 134.4, 133.1, 129.5, 129.3, 129.1, 128.5, 128.4, 126.5, 126.2, 119.8, 68.7, 32.4, 28.8, 21.5, 21.2; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H26O2SNa: 413.1551; found: 413.1544. (E)-1-Methoxy-4-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-3). Yellow solid (36.3 mg, 45%), mp: 125−127 °C; PE/EA = 18/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.28− 7.19(m, 7H), 7.13−7.11(m, 2H), 6.85(d, J = 8.8 Hz, 2H), 6.23(d, J = 16.0 Hz, 1H), 5.78(dd, J = 9.2 Hz, 16.0 Hz, 1H), 3.81(s, 3H), 3.62− 3.56(m, 1H), 2.83−2.78(m, 1H), 2.60−2.50(m, 2H), 2.40(s, 3H), 2.07−2.01(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 159.78, 144.4, 140.1, 137.9, 134.5, 129.4, 129.1, 128.6, 128.5, 128.4, 127.8, 126.2, 118.4, 114.0, 68.8 55.3, 32.4, 28.9, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H26O3SNa: 429.1500; found: 429.1495. (E)-Methyl(4-(5-phenyl-3-tosylpent-1-en-1-yl)phenyl)sulfane (3-4). Yellow solid (39.7 mg, 47%), mp: 110−113 °C; PE/EA = 17/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.28− 7.22(m, 4H), 7.20−7.17(m, 5H), 7.11(d, J = 7.2 Hz, 2H), 6.23(d, J = 16.0 Hz, 1H), 5.91−5.85(m, 1H), 3.63−3.58(m, 1H), 2.83−2.76 (m, 1H), 2.59−2.53(m, 2H), 2.49(s, 3H), 2.40(s, 3H), 2.08−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.5, 140.0, 139.1, 137.7, 134.4, 132.6, 129.4, 129.1, 128.5, 128.4, 126.9, 126.3, 120.1, 68.7, 32.4, 28.8, 21.6, 15.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H26O2S2Na: 445.1272; found:445.1264. (E)-1-Methyl-4-((5-phenyl-1-(4-(trifluoromethyl)phenyl)pent-1en-3-yl)sulfonyl)benzene (3-5). Yellow solid (74.6 mg, 84%), mp: 95− 97 °C; PE/EA = 18/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.66(d, J = 8.4 Hz, 2H), 7.57(d, J = 8.4 Hz, 2H), 7.37(d, J = 8.0 Hz, 2H), 7.29− 7.25(m, 4H), 7.21−7.18(m, 1H), 7.13−7.10(m, 2H), 6.32(d, J = 16.0 Hz, 1H), 6.04(dd, J = 9.2 Hz, J = 16.0 Hz, 1H), 3.68−3.62(m, 1H), 2.84− 2.76(m, 1H), 2.63−2.52(m, 2H), 2.41(s, 3H), 2.12−2.07(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.8, 139.8, 139.1, 136.9, 134.3, 129.5, 129.1, 128.5, 128.4, 126.7, 126.4, 125.7, 125.6, 125.5, 125.5, 123.9, 68.5, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H23F3O2SNa: 467.1269; found: 467.1266. (E)-1-Fluoro-4-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-6). Yellow solid (65.4 mg, 83%), mp: 86−89 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.27−7.24(m, 6H), 7.21−7.19(m, 1H), 7.12−7.10(m, 2H), 7.01(t, J = 8.8 Hz, 2H), 6.26(d, J = 16.0 Hz, 1H), 5.88−5.82(m, 1H), 3.64−3.58(m, 1H), 2.83−2.78(m, 1H), 2.59−2.50(m, 2H), 2.40(s, 3H), 2.09−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.6, 139.9, 137.2, 134.4, 132.0, 131.9, 129.5, 129.1, 128.5, 128.4, 128.3, 128.2, 128.1, 126.3, 120.7, 120.6, 115.7, 115.5, 68.6, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23FO2SNa: 417.1300; found: 417.1293. (E)-1-Chloro-4-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-7). Yellow solid (60.7 mg, 74%), mp: 84−86 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.30−7.24(m, 6H), 7.22−7.19(m, 3H), 7.12−7.10(m, 2H), 6.24(d, J = 16.0 Hz, 1H), 5.90(dd, J = 9.6 Hz, J = 16.0 Hz, 1H), 3.64−3.58(m, 1H), 2.80−2.75(m, 1H), 2.59−2.51(m, 2H), 2.40(s, 3H), 2.09−2.01(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.6, 139.9, 137.0, 134.3, 134.2, 134.1, 129.4, 129.1, 128.8, 128.5, 128.3, 127.7, 126.3, 121.6, 68.5, 32.4, 28.8, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23ClO2SNa: 433.1005; found: 433.0999.

a

Reaction conditions: 1a (0.2 mmol, 1.0 equiv), 2 (0.45 mmol, 2.25 equiv), Pd(OAc)2 (10 mol %), PPh3 (30 mol %), K2CO3 (0.6 mmol, 3.0 equiv), BTAC (0.2 mmol, 1.0 equiv), dioxane (2 mL), Ar, at 30 °C for 45 min then 70 °C for 12 h. Yield is of the isolated product. bThis reaction was carried out with addition of 2.0 equiv of corresponding sodium sulfinate salt. cNMR yield.

Scheme 3. Palladium-Catalyzed Cross-Coupling of Vinyl Iodide 1b with N-Tosylhydrazone 2aa

a Reaction conditions: 1b (0.2 mmol, 1.0 equiv), 2a (0.45 mmol, 2.25 equiv), Pd(OAc)2 (10 mol %), PPh3 (30 mol %), K2CO3 (0.6 mmol, 3.0 equiv), BTAC (0.2 mmol, 1.0 equiv), dioxane (2 mL), Ar, at 30 °C for 45 min then 70 °C for 12 h. Yield is of the isolated product.

Scheme 4. Proposed Catalytic Cycle

through Celite, eluting with EtOAc. The volatiles were evaporated under reduced pressure, and the residue was purified by silica gel flash chromatography to afford the desired products 3. 4765

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768

Article

The Journal of Organic Chemistry

(ESI-TOF) m/z: [M + Na]+, calcd for C25H26O2SNa: 413.1551; found: 413.1548. (E)-1-Fluoro-2-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-15). Yellow solid (59.9 mg, 76%), mp: 89−92 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.67(d, J = 8.0 Hz, 2H), 7.39−7.35(m, 1H), 7.28−7.26(m, 5H), 7.24−7.19(m, 1H), 7.14−7.09(m, 3H), 7.05− 7.00(m, 1H), 6.42(d, J = 16.4 Hz, 1H), 6.04(dd, J = 9.2 Hz, J = 16.0 Hz, 1H), 3.66−3.60(m, 1H), 2.85−2.79(m, 1H), 2.60−2.52(m, 2H), 2.41(s, 3H), 2.10−2.02(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.7, 139.9, 134.3, 130.9, 130.8, 130.8, 129.7, 129.5, 129.4, 129.1, 128.5, 128.5, 128.4, 127.6, 127.5, 126.3, 124.2, 124.1, 123.8, 123.7, 123.7, 115.9, 115.7, 69.0, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23FO2SNa: 417.1300; found: 417.1299. (E)-1-Chloro-2-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-16). NMR Yield (77%); yellow solid, mp: 73−76 °C; NMR yield; PE/EA = 20/1 as eluent; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23ClO2SNa: 433.1005; found: 433.1004. (E)-1-Bromo-2-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-17). Yellow solid (74.5 mg, 82%), mp: 71−73 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.67(d, J = 8.0 Hz, 2H), 7.51(d, J = 8.4 Hz, 1H), 7.44−7.42(m, 1H), 7.30−7.25(m, 5H), 7.20(d, J = 7.2 Hz, 1H), 7.17−7.13(m, 3H), 6.57(d, J = 15.6 Hz, 1H), 5.95−5.88(m, 1H), 3.70−3.64(m, 1H), 2.88−2.82(m, 1H), 2.63−2.55(m, 2H), 2.40(s, 3H), 2.16−2.10(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.7, 139.9, 137.1, 135.8, 134.3, 132.9, 129.6, 129.5, 129.0, 128.5, 128.4, 127.6, 127.3, 126.3, 124.2, 123.5, 68.4, 32.3, 28.5, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23BrO2SNa: 477.0500; found: 477.0502. (E)-2-(5-Phenyl-3-tosylpent-1-en-1-yl)naphthalene (3-18). Yellow solid (60.5 mg, 71%), mp: 109−112 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.81−7.77(m, 3H), 7.68(d, J = 8.0 Hz, 2H), 7.62(s, 1H), 7.52−7.45(m, 3H), 7.29−7.20(m, 5H), 7.15−7.13(m, 2H), 6.43(d, J = 16.0 Hz, 1H), 6.10−6.04(m, 1H), 3.71−3.65(m, 1H), 2.87−2.80(m, 1H), 2.65−2.56(m, 2H), 2.38(s, 3H), 2.15−2.10(m, 1H); 13 C NMR (100 MHz, CDCl3) δ: 144.5, 140.1, 138.4, 134.4, 133.3, 133.2, 133.2, 129.4, 129.2, 128.5, 128.4, 128.3, 128.0, 127.6, 126.9, 126.5, 126.3, 126.3, 123.2, 121.3, 68.8, 32.5, 28.8, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C28H26O2SNa: 449.1551; found: 449.1547. (E)-1-(5-Phenyl-3-tosylpent-1-en-1-yl)naphthalene (3-19). Yellow solid (71.6 mg, 84%), mp: 107−109 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.84−7.78(m, 2H), 7.71(d, J = 8.4 Hz, 2H), 7.60(d, J = 8.0 Hz, 1H), 7.49−7.42(m, 4H), 7.29−7.17(m, 7H), 6.95(d, J = 15.6 Hz, 1H), 5.97(dd, J = 9.6 Hz, J = 15.6 Hz, 1H), 3.79− 3.73(m, 1H), 2.93−2.86(m, 1H), 2.70−2.64m, 2H), 2.38(s, 3H), 2.21− 2.17(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.5, 139.9, 136.1, 134.5, 133.6, 133.4, 130.7, 129.5, 129.1, 128.7, 128.5, 128.5, 128.4, 126.3, 126.1, 125.9, 125.5, 124.4, 124.1, 123.4, 68.9, 32.5, 28.4, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C28H26O2SNa: 449.1551; found: 449.1552. (E)-2-(5-Phenyl-3-tosylpent-1-en-1-yl)furan (3-20). Yellow oil (30.7 mg, 42%); PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.66(d, J = 8.4 Hz, 2H), 7.36(d, J = 1.6 Hz, 1H), 7.29− 7.24(m, 4H), 7.19(d, J = 7.2 Hz, 1H), 7.12−7.10(m, 2H), 6.37(dd, J = 1.6 Hz, J = 3.2 Hz, 1H), 6.23(d, J = 3.2 Hz, 1H), 6.17(d, J = 16.0 Hz, 1H), 5.90−5.84(m, 1H), 3.60−3.54(m, 1H), 2.83−2.77(m, 1H), 2.57− 2.47(m, 2H), 2.41(s, 3H), 2.03−1.94(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 151.4, 144.6, 142.7, 140.0, 134.3, 129.5, 129.2, 128.5, 128.4, 126.3, 126.2, 119.0, 111.4, 109.5, 68.5, 32.4, 29.1, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C22H22O3SNa: 389.1187; found: 389.1180. (E)-2,4-Dichloro-1-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-21). Yellow solid (64.8 mg, 73%), mp: 91−93 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.37− 7.34(m, 2H), 7.29−7.25(m, 4H), 7.23−7.20(m, 2H), 7.13(d, J = 6.8 Hz, 2H), 6.53(d, J = 15.6 Hz, 1H), 5.97−5.91(m, 1H), 3.69−3.63(m, 1H), 2.85−2.80(m, 1H), 2.62−2.52(m, 2H), 2.41(s, 3H), 2.15−2.07(m, 1H); 13 C NMR (100 MHz, CDCl3) δ: 144.8, 139.8, 134.5, 134.2, 133.6, 133.5, 132.6, 129.5, 129.4, 129.0, 128.5, 128.4, 127.8, 127.4, 126.3, 124.6, 68.5, 32.4, 28.5, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H22Cl2O2SNa: 467.0615; found: 467.0609.

(E)-1-Bromo-4-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-8). Yellow oil (52.7 mg, 58%); PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.44(d, J = 8.4 Hz, 2H), 7.28−7.25(m, 4H), 7.20(d, J = 7.2 Hz, 1H), 7.15−7.10(m, 4H), 6.23(d, J = 16.0 Hz, 1H), 5.92(dd, J = 9.2 Hz, J = 16.0 Hz,1H), 3.63− 3.58(m, 1H), 2.83−2.75(m, 1H), 2.61−2.50(m, 2H), 2.41(s, 3H), 2.09−2.01(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.7, 139.9, 137.1, 134.7, 134.4, 131.8, 129.5, 129.1, 128.5, 128.4, 128.0, 126.3, 122.4, 121.8, 68.6, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23BrO2SNa: 477.0500; found: 477.0499. (E)-1-Methyl-3-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-9). Yellow oil (48.4 mg, 62%); PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.66(d, J = 8.0 Hz, 2H), 7.28−7.25(d, J = 8.4 Hz, 4H), 7.23−7.20(m, 2H), 7.13−7.07(m, 5H), 6.25(d, J = 16.0 Hz, 1H), 5.96−5.90(m, 1H), 3.63−3.58(m, 1H), 2.84−2.77(m, 1H), 2.61− 2.50(m, 2H), 2.40(s, 3H), 2.35(s, 3H), 2.10−2.05(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.5, 140.0, 138.5, 138.3, 135.8, 134.5, 129.4, 129.2, 129.1, 128.5, 128.4, 127.2, 126.3, 123.8, 120.7, 68.7, 32.4, 28.8, 21.6, 21.3; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H26O2SNa: 413.1551; found: 413.1546. (E)-1-Methoxy-3-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-10). Yellow oil (47.9 mg, 59%); PE/EA = 18/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.66(d, J = 8.4 Hz, 2H), 7.28−7.24(m, 5H), 7.22−7.19(m, 1H), 7.13−7.11(m, 2H), 6.89−6.82(m, 3H), 6.25(d, J = 15.6 Hz, 1H), 5.96−5.90(m,1H), 3.81(s, 3H), 3.64−3.58(m, 1H), 2.82−2.77(m, 1H), 2.60−2.52(m, 2H), 2.40(s, 3H), 2.09−2.05(m, 1H); 13 C NMR (100 MHz, CDCl3) δ: 159.8, 144.6, 140.0, 138.3, 137.2, 134.4, 129.6, 129.4, 129.1, 128.5, 128.4, 126.3, 121.3, 119.2, 114.0, 111.9, 68.6, 55.2, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H26O3SNa: 429.1500; found: 429.1499. (E)-1-Fluoro-3-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-11). Yellow solid (64.6 mg, 82%), mp: 87−89 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 16.0 Hz, 2H), 7.28− 7.24(m, 5H), 7.19(d, J = 7.2 Hz, 1H), 7.12−7.10(m, 2H), 7.04(d, J = 8.0 Hz, 1H), 6.99−6.96(m, 2H), 6.26(d, J = 15.6 Hz, 1H), 5.97− 5.91(m,1H), 3.65−3.59(m, 1H), 2.81−2.75(m, 1H), 2.59−2.51(m, 2H), 2.40(s, 3H), 2.09−2.03(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.7, 139.8, 138.1, 138.0, 137.2, 137.1, 134.3, 130.2, 130.1, 129.5, 129.1, 128.5, 128.3, 126.3, 122.5, 122.4, 122.4, 115.3, 115.1, 113.1, 112.9, 68.5, 32.4, 28.8, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23FO2SNa: 417.1300; found: 417.1296. (E)-1-Chloro-3-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-12). Yellow solid (64.0 mg, 78%), mp: 98−100 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.0 Hz, 2H), 7.28− 7.24(m, 7H), 7.21−7.19(m, 1H), 7.17−7.14(m, 1H), 7.12−7.10(m, 2H), 6.22(d, J = 16.0 Hz, 1H), 5.98−5.92(m,1H), 3.64−3.58(m, 1H), 2.83− 2.75(m, 1H), 2.61−2.51(m, 2H), 2.41(s, 3H), 2.10−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.7, 139.8, 137.6, 136.9, 134.6, 134.3, 129.9, 129.5, 129.1, 128.5, 128.4, 128.3, 126.4, 126.3, 124.7, 122.7, 68.5, 32.4, 28.8, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23ClO2SNa: 433.1005; found: 433.0996. (E)-1-Bromo-3-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-13). Yellow solid (76.3 mg, 84%), mp: 78−81 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.41−7.38(m, 2H), 7.27−7.24(m, 4H), 7.20−7.17(m, 3H), 7.12−7.10(m, 2H), 6.22(d, J = 16.0 Hz, 1H), 5.97−5.91(m, 1H), 3.65−3.59(m, 1H), 2.82−2.75(m, 1H), 2.59−2.51(m, 2H), 2.40(s, 3H), 2.10−2.04(m, 1H); 13 C NMR (100 MHz, CDCl3) δ: 144.7, 139.8, 137.8, 136.8, 134.2, 131.2, 130.1, 129.5, 129.3, 129.0, 128.5, 128.3, 126.3, 125.1, 122.7, 122.6, 68.5, 32.4, 28.7, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H23BrO2SNa: 477.0500; found:477.0494. (E)-1-Methyl-2-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-14). Yellow solid (49.9 mg, 64%), mp: 92−94 °C; PE/EA = 20/1 as eluent; 1 H NMR (400 MHz, CDCl3) δ: 7.70(m, 2H), 7.35(t, J = 4.4 Hz, 1H), 7.25(t, J = 8.0 Hz, 4H), 7.20−7.13(m, 6H), 6.50−6.45(m, 1H), 5.86− 5.78(m,1H), 3.69−3.62(m, 1H), 2.85−2.81(m, 1H), 2.63−2.57(m, 2H), 2.38(s, 3H), 2.13−2.08(m, 4H); 13C NMR (100 MHz, CDCl3) δ: 144.5, 140.0, 136.5, 135.5, 135.0, 134.5, 130.2, 129.4, 129.1, 128.5, 128.4, 128.2, 126.2, 126.1, 125.8, 122.4, 68.8, 32.4, 28.5, 21.5, 19.4; HRMS 4766

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768

Article

The Journal of Organic Chemistry

2.15−2.09(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 139.9, 138.5, 135.4, 130.8, 128.8, 128.5, 128.4, 127.4, 126.7, 126.3, 121.4, 64.8, 56.9, 32.2, 27.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H24O2SNa: 399.1395; found: 399.1390. (E)-2-((1,5-Diphenylpent-1-en-3-yl)sulfonyl)thiophene (3-30). Yellow solid (42.0 mg, 57%), mp: 93−95 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(dd, J = 1.2 Hz, J = 5.2 Hz, 1H), 7.56(dd, J = 1.2 Hz, J = 3.6 Hz, 1H), 7.34−7.24(m, 7H), 7.20(d, J = 6.8 Hz, 1H), 7.13(d, J = 6.8 Hz, 2H), 7.08(dd, J = 3.6 Hz, J = 4.8 Hz, 1H), 6.38(d, J = 16.0 Hz, 1H), 6.04−5.98(m, 1H), 3.74−3.69(m, 1H), 2.87− 2.80(m, 1H), 2.65−2.57(m, 2H), 2.16−2.10(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 139.9, 138.8, 138.1, 135.7, 135.1, 134.3, 128.7, 128.5, 128.4, 127.6, 126.7, 126.3, 120.7, 69.8, 32.4, 28.9; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C21H20O2S2Na: 391.0802; found: 391.0798. (E)-(3-Methyl-3-tosylpent-1-ene-1,5-diyl)dibenzene (3-31). Yellow oil (55.4 mg, 71%); PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.65(d, J = 8.4 Hz, 2H), 7.34(d, J = 8.4 Hz, 4H), 7.31− 7.22(m, 5H), 7.20−7.15(m, 3H), 6.34(d, J = 16.4 Hz, 1H), 6.24(d, J = 16.4 Hz, 1H), 2.67−2.52(m, 2H), 2.39(s, 3H), 2.36−2.31(m, 2H), 1.56(s, 3H); 13C NMR (100 MHz, CDCl3) δ: 144.5, 141.0, 136.0, 134.9, 132.3, 130.6, 129.0, 128.7, 128.4, 128.3, 128.3, 126.6, 126.4, 126.1, 68.0, 35.1, 30.3, 21.5, 17.1; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C25H26O2SNa: 413.1551; found: 413.1548.

(E)-1,2-Dichloro-4-(5-phenyl-3-tosylpent-1-en-1-yl)benzene (3-22). Yellow solid (76.4 mg, 86%), mp: 86−88 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.64(d, J = 8.0 Hz, 2H), 7.37(d, J = 8.4 Hz, 1H), 7.32(d, J = 2.0 Hz, 1H), 7.28−7.24(m, 4H), 7.19(d, J = 7.2 Hz, 1H), 7.11−7.09(m, 3H), 6.18(d, J = 16.0 Hz, 1H), 5.97−5.90(m, 1H), 3.64−3.56(m, 1H), 2.82−2.76(m, 1H), 2.59−2.50(m, 2H), 2.41(s, 3H), 2.10−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 144.8, 139.7, 135.9, 135.7, 134.2, 132.8, 132.1, 130.5, 129.5, 129.0, 128.5, 128.3, 128.2, 126.3, 125.6, 123.1, 68.4, 32.4, 28.7, 21.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H22Cl2O2SNa: 467.0615; found: 467.0615 (E)-(3-(Phenylsulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-23). Yellow solid (47.1 mg, 65%), mp: 70−73 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.80−7.78(m, 2H), 7.58(t, J = 7.6 Hz, 1H), 7.49−7.45(m, 2H), 7.34−7.24(m, 7H), 7.21−7.18(m, 1H), 7.12(d, J = 6.8 Hz, 2H), 6.25(d, J = 16.0 Hz, 1H), 5.98−5.91(m, 1H), 3.67−3.61(m, 1H), 2.82−2.80(m, 1H), 2.60−2.53(m, 2H), 2.12−2.08(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 139.9, 138.6, 137.3, 135.7, 133.6, 129.1, 128.8, 128.6, 128.5, 128.4, 128.3, 126.5, 126.3, 120.8, 68.6, 32.4, 28.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C23H22O2SNa: 385.1238; found: 385.1239. (E)-(3-((4-Chlorophenyl)sulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-24). Yellow solid (52.3 mg, 66%), mp: 68−71 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.71(d, J = 8.4 Hz, 2H), 7.44(dd, J = 2.0 Hz, J = 6.8 Hz, 2H), 7.34−7.28(m, 7H), 7.21−7.18(m, 1H), 7.13−7.12(m, 2H), 6.27(d, J = 16.0 Hz, 1H), 5.93(dd, J = 9.6 Hz, J = 16.0 Hz, 1H), 3.65−3.59(m, 1H), 2.86−2.79(m, 1H), 2.60−2.52(m, 2H), 2.12−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 140.4, 139.8, 138.7, 135.9, 135.5, 130.6, 129.1, 128.7, 128.6, 128.5, 128.4, 126.6, 126.4, 120.5, 68.7, 32.3, 28.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C23H21ClO2SNa: 419.0848; found: 419.0846. (E)-(3-((4-Methoxyphenyl)sulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-25). Yellow solid (63.6 mg, 81%), mp: 75−77 °C; PE/EA = 17/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.70(dd, J = 2.0 Hz, J = 6.8 Hz, 2H), 7.32−7.23(m, 7H), 7.19(d, J = 7.2 Hz, 1H), 7.14−7.12(m, 2H), 6.91(dd, J = 2.0 Hz, J = 7.2 Hz, 2H), 6.28(d, J = 16.0 Hz, 1H), 5.98− 5.91(m, 1H), 3.82(s, 3H), 3.64−3.58(m, 1H), 2.82−2.78(m, 1H), 2.60−2.52(m, 2H), 2.08−2.04(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 163.6, 140.0, 138.3, 135.8, 131.2, 128.8, 128.6, 128.5, 128.4, 126.5, 126.2, 121.1, 114.0, 68.8, 55.6, 32.4, 28.9; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H24O3SNa: 415.1344; found: 415.1343. (E)-(3-(m-Tolylsulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-26). Yellow solid (49.6 mg, 66%), mp: 86−88 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.57(d, J = 5.2 Hz, 2H), 7.39−7.23(m, 9H), 7.21−7.17(m, 1H), 7.11(d, J = 7.2 Hz, 2H), 6.26(d, J = 16.0 Hz, 1H), 5.97−5.91(m, 1H), 3.65−3.59(m, 1H), 2.85−2.77(m, 1H), 2.60− 2.51(m, 2H), 2.33(s, 3H), 2.12−2.06(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 134.0, 139.0, 138.5, 137.1, 135.8, 134.3, 129.5, 128.6, 128.5, 128.4, 128.3, 126.5, 126.3, 120.9, 68.6, 32.4, 28.6, 21.1; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H24O2SNa: 399.1395; found: 399.1394. (E)-(3-((3-Fluorophenyl)sulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-27). Yellow solid (41.8 mg, 55%), mp: 98−101 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.57(d, J = 8.0 Hz, 1H), 7.53− 7.50(m, 1H), 7.48−7.42(m, 1H), 7.33−7.20(m, 9H), 7.12(d, J = 6.8 Hz, 2H), 6.28(d, J = 15.6 Hz, 1H), 5.97−5.91(m, 1H), 3.67−3.61(m, 1H), 2.87−2.81(m, 1H), 2.61−2.52(m, 2H), 2.14−2.08(m, 1H); 13C NMR (100 MHz, CDCl3) δ: 139.7, 139.5, 139.0, 135.5, 130.6, 130.5, 128.7, 128.6, 128.5, 128.4, 126.6, 126.4, 125.0, 125.0, 121.0, 120.8, 120.4, 116.5, 116.2, 68.7, 32.3, 28.6; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C23H21FO2SNa: 403.1144; found: 403.1141. (E)-(3-(o-Tolylsulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-28). NMR yield; yellow solid (67%), mp: 70−74 °C; NMR yield; PE/EA = 20/1 as eluent; HRMS (ESI-TOF) m/z: [M + Na]+, calcd for C24H24O2SNa: 399.1395; found: 399.1391. (E)-(3-(Benzylsulfonyl)pent-1-ene-1,5-diyl)dibenzene (3-29). Yellow solid (40.6 mg, 54%), mp: 78−81 °C; PE/EA = 20/1 as eluent; 1H NMR (400 MHz, CDCl3) δ: 7.46−7.44(m, 2H), 7.41−7.33(m, 8H), 7.27−7.24(m, 2H), 7.20−7.18(m, 1H), 7.11(d, J = 7.2 Hz, 2H), 6.56(d, J = 16.0 Hz, 1H), 6.17(dd, J = 8.0 Hz, J = 16.0 Hz, 1H), 4.25−4.17(m, 2H), 3.60−3.54(m, 1H), 2.81−2.78(m, 1H), 2.57−2.49(m, 2H),

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.8b00615. Copies of 1H, 13C spectra for new compounds (PDF) Crystallographic data for compound 3-1 (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (P.-X.Z.). *E-mail: [email protected] (C.L.). *E-mail: [email protected] (Y.-M.L.). ORCID

Ping-Xin Zhou: 0000-0003-4589-9171 Yong-Min Liang: 0000-0001-8280-8211 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by grants from the National Natural Science Foundation of China (21702177), Key Scientific Research Project of Higher Education of Henan Province, China (18A150045), and the program of China Scholarships Council (201708410040)

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REFERENCES

(1) (a) Simpkins, N. S. Sulfones in Organic Synthesis; Pergamon: Oxford, U.K., 1993. (b) Taylor, R. J. K.; Casy, G. The RambergBäcklund Reaction. Organic Reactions; John Wiley & Sons, Inc.: Hoboken, NJ, 2003; Vol. 62, p 357. (c) Plesniak, K.; Zarecki, A.; Wicha, J. The Smiles Rearrangement and the Julia-kocienski Olefination Reaction. Top. Curr. Chem. 2006, 275, 163. (d) El-Awa, A.; NoShi, M. N.; du Jourdin, X. M.; Fuchs, P. L. Evolving Organic Synthesis Fostered by the Pluripotent Phenylsulfone Moiety. Chem. Rev. 2009, 109, 2315. (e) Alba, A. R.; Companyó, X.; Rios, R. Sulfones: New Reagents in Organocatalysis. Chem. Soc. Rev. 2010, 39, 2018. (2) (a) Reck, F.; Zhou, F.; Girardot, M.; Kern, G.; Eyermann, C. J.; Hales, N. J.; Ramsay, R. R.; Gravestock, M. B. Identification of 4Substituted 1,2,3-Triazoles as Novel Oxazolidinone Antibacterial Agents with Reduced Activity against Monoamine Oxidase A. J. Med. Chem. 2005, 48, 499. (b) Pabba, C.; Gregg, B. T.; Kitchen, D. B.; Chen, 4767

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768

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Valdés, C. Pd-Catalyzed Cascade Reactions between o-iodo-Nalkenylanilines and Tosylhydrazones: Novel Approaches to the Synthesis of Polysubstituted Indoles and 1,4-Dihydroquinolines. Chem. Commun. 2016, 52, 6312. (g) Xia, Y.; Hu, F.; Xia, Y.; Liu, Z.; Ye, F.; Zhang, Y.; Wang, J. Synthesis of Di- and Triarylmethanes through Palladium-Catalyzed Reductive Coupling of N-Tosylhydrazones and Aryl Bromides. Synthesis 2017, 49, 1073. (7) (a) Zhang, Z.; Liu, Y.; Gong, M.; Zhao, X.; Zhang, Y.; Wang, J. Palladium-Catalyzed Carbonylation/Acyl Migratory Insertion Sequence. Angew. Chem., Int. Ed. 2010, 49, 1139. (b) Zhou, P.-X.; Zhou, Z.-Z.; Chen, Z.-S.; Ye, Y.-Y.; Zhao, L.-B.; Yang, Y.-F.; Xia, X.-F.; Luo, J.Y.; Liang, Y.-M. Palladium-Catalyzed Insertion of α-diazocarbonyl Compounds for the Synthesis of Cyclic Amino Esters. Chem. Commun. 2013, 49, 561. (c) Arunprasath, D.; Bala, B. D.; Sekar, G. Stereoselective Construction of α-Tetralone-Fused Spirooxindoles via Pd-Catalyzed Domino Carbene Migratory Insertion/Conjugate Addition Sequence. Org. Lett. 2017, 19, 5280. (8) (a) Zhou, P.-X.; Luo, J.-Y.; Zhao, L.-B.; Ye, Y.-Y.; Liang, Y.-M. Palladium-Catalyzed Insertion of N-tosylhydrazones for the Synthesis of Isoindolines. Chem. Commun. 2013, 49, 3254. (b) Ye, Y.-Y.; Zhou, P.-X.; Luo, J.-Y.; Zhong, M.-J.; Liang, Y.-M. Palladium-Catalyzed Insertion of α,β-unsaturated N-tosylhydrazones and Trapping with Carbon Nucleophiles. Chem. Commun. 2013, 49, 10190. (c) Zhou, P.-X.; Ye, Y.-Y.; Zhao, L.-B.; Hou, J.-Y.; Kang, X.; Chen, D.-Q.; Tang, Q.; Zhang, J.Y.; Huang, Q.-X.; Zheng, L.; Ma, J.-W.; Xu, P.-F.; Liang, Y.-M. Using Ntosylhydrazone as a Double Nucleophile in the Palladium-Catalyzed Cross-Coupling Reaction to Synthesize Allylic Sulfones. Chem. - Eur. J. 2014, 20, 16093. (9) (a) Khanna, A.; Maung, C.; Johnson, K. R.; Luong, T. T.; Van Vranken, D. L. Carbenylative Amination with N-Tosylhydrazones. Org. Lett. 2012, 14, 3233. (b) Zhou, P.-X.; Ye, Y.-Y.; Liang, Y.-M. PalladiumCatalyzed Insertion of N-tosylhydrazones and Trapping with Carbon Nucleophiles. Org. Lett. 2013, 15, 5080. (c) Xia, Y.; Xia, Y.; Zhang, Y.; Wang, J. Palladium-Catalyzed Coupling of N-Tosylhydrazones and βbromostyrene Derivatives: New Approach to 2H-chromenes. Org. Biomol. Chem. 2014, 12, 9333. (d) Premachandra, I. D. U. A.; Nguyen, T. A.; Shen, C.; Gutman, E. S.; Van Vranken, D. L. Carbenylative Amination and Alkylation of Vinyl Iodides via Palladium Alkylidene Intermediates. Org. Lett. 2015, 17, 5464. (10) (a) Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M. Unsymmetrical Diaryl Sulfones through Palladium-Catalyzed Coupling of Aryl Iodides and Arenesulfinates. Org. Lett. 2002, 4, 4719. (b) Cacchi, S.; Fabrizi, G.; Goggiamani, A.; Parisi, L. M.; Bernini, R. Unsymmetrical Diaryl Sulfones and Aryl Vinyl Sulfones through Palladium-Catalyzed Coupling of Aryl and Vinyl Halides or Triflates with Sulfinic Acid Salts. J. Org. Chem. 2004, 69, 5608. (11) (a) Chen, Z.-S.; Duan, X.-H.; Wu, L.-Y.; Ali, S.; Ji, K.-G.; Zhou, P.X.; Liu, X.-Y.; Liang, Y.-M. Palladium-Catalyzed Coupling of Propargylic Carbonates with N-tosylhydrazones: Highly Selective Synthesis of Substituted Propargylic N-sulfonylhydrazones and Vinylallenes. Chem. Eur. J. 2011, 17, 6918. (b) Chen, Z.-S.; Duan, X.-H.; Zhou, P.-X.; Ali, S.; Luo, J.-Y.; Liang, Y.-M. Palladium-Catalyzed Divergent Reactions of αdiazocarbonyl Compounds with Allylic Esters: Construction of Quaternary Carbon Centers. Angew. Chem., Int. Ed. 2012, 51, 1370. (c) Zhou, P.-X.; Zheng, L.; Ma, J.-W.; Ye, Y.-Y.; Liu, X.-Y.; Xu, P.-F.; Liang, Y.-M. Palladium-Catalyzed/Norbornene-mediated C-H Activation/N-tosylhydrazone Insertion Reaction: a Route to Highly Functionalized Vinylarenes. Chem. - Eur. J. 2014, 20, 6745. (12) Denmark, S. E.; Wang, Z. Palladium Catalyzed Cross-Coupling of (Z)-1-Heptenyldimethylsilanol with 4-Iodoanisole: (Z)-1-Heptenyl-4methoxybenzene. Org. Synth 2005, 81, 42. (13) Negishi, E.; Van Horn, D. E.; Yoshida, T. Controlled Carbometalation. 20. Carbometalation Reaction of Alkynes with Organoalene-zirconocene Derivatives as a Route to Stereo-and Regiodefined Trisubstituted Alkenes. J. Am. Chem. Soc. 1985, 107, 6639. (14) Fulton, J. R.; Aggarwal, V. K.; de Vicente, J. The Use of Tosylhydrazone Salts as a Safe Alternative for Handling Diazo Compounds and Their Applications in Organic Synthesis. Eur. J. Org. Chem. 2005, 2005, 1479.

Z. J.; Judkins, A. Design and Synthesis of Aryl Ether and Sulfone Hydroxamic Acids as Potent Histone Deacetylase (HDAC) Inhibitors. Bioorg. Med. Chem. Lett. 2011, 21, 324. (c) Chen, X.; Hussain, S.; Parveen, S.; Zhang, S.; Yang, Y.; Zhu, C. Sulfonyl Group-Containing Compounds in the Design of Potential Drugs for the Treatment of Diabetes and Its Complications. Curr. Med. Chem. 2012, 19, 3578. (3) (a) Solladie, G. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, U.K., 1991; Vol. 6, p 133. (b) Procter, D. J. The Synthesis of Thiols, Selenols, Sulfides, Selenides, Sulfoxides, Selenoxides, Sulfones and Selenones. J. Chem. Soc., Perkin Trans. 1 2001, 335. (c) Choi, S.; Yang, J.-D.; Ji, M.; Choi, H.; Kee, M.; Ahn, K.-H.; Byeon, S.-H.; Baik, W.; Koo, S. Selective Oxidation of Allylic Sulfides by Hydrogen Peroxide with the Trirutile-type Solid Oxide Catalyst LiNbMoO6. J. Org. Chem. 2001, 66, 8192. (d) Chandrasekhar, S.; Jagadeshwar, V.; Saritha, B.; Narsihmulu, C. Palladium-Triethylborane-Triggered Direct and Regioselective Conversion of Allylic Alcohols to Allyl Phenyl Sulfones. J. Org. Chem. 2005, 70, 6506. (e) Gais, H.-J. In Asymmetric Synthesis with Chemical and Biological Methods; Enders, D., Jäger, K.-E., Eds.; Wiley-VCH: Weinheim, Germany, 2007; p 215. (f) Reddy, M. A.; Reddy, P. S.; Sreedhar, B. Iron(III) ChlorideCatalyzed Direct Sulfonylation of Alcohols with Sodium Arenesulfinates. Adv. Synth. Catal. 2010, 352, 1861. (g) Ueda, M.; Hartwig, J. F. Iridium-Catalyzed, Regio- and Enantioselective Allylic Substitution with Aromatic and Aliphatic Sulfinates. Org. Lett. 2010, 12, 92. (4) (a) Xiao, Q.; Zhang, Y.; Wang, J. Diazo Compounds and NTosylhydrazones: Novel Cross-Coupling Partners in Transition-MetalCatalyzed Reactions. Acc. Chem. Res. 2013, 46, 236. (b) Xia, Y.; Wang, J. N-Tosylhydrazones: Versatile Synthons in the Construction of Cyclic Compounds. Chem. Soc. Rev. 2017, 46, 2306. (c) Xia, Y.; Qiu, D.; Wang, J. Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion. Chem. Rev. 2017, 117, 13810 and references therein. (5) For recent work on palladium-catalyzed insertion diazo compound, followed by β-hydride elimination, see: (a) Zhou, Y.; Ye, F.; Wang, X.; Xu, S.; Zhang, Y.; Wang, J. Synthesis of Alkenylphosphonates through Palladium-Catalyzed Coupling of α-Diazo Phosphonates with Benzyl or Allyl Halides. J. Org. Chem. 2015, 80, 6109. (b) Luo, H.; Wu, G.; Xu, S.; Wang, K.; Wu, C.; Zhang, Y.; Wang, J. Palladium-Catalyzed CrossCoupling of Aryl Fluorides with N-tosylhydrazones via C-F Bond Activation. Chem. Commun. 2015, 51, 13321. (c) Wang, K.; Chen, S.; Zhang, H.; Xu, S.; Ye, F.; Zhang, Y.; Wang, J. Pd(0)-Catalyzed CrossCoupling of Allyl Halides with α-diazocarbonyl Compounds or Nmesylhydrazones: Synthesis of 1,3-Diene Compounds. Org. Biomol. Chem. 2016, 14, 3809. (d) Ngo, T. N.; Dang, T. T.; Villinger, A.; Langer, P. Regioselective Synthesis of Naphtho-fused Heterocycles via Palladium(0)-Catalyzed Tandem Reaction of N-Tosylhydrazones. Adv. Synth. Catal. 2016, 358, 1328. (e) Mao, M.; Zhang, L.; Chen, Y.Z.; Zhu, J.; Wu, L. Palladium-Catalyzed Coupling of Allenylphosphine Oxides with N-Tosylhydrazones toward Phosphinyl [3]Dendralenes. ACS Catal. 2017, 7, 181. (f) Paraja, M.; Valdés, C. Pd-Catalyzed Autotandem Reactions with N-Tosylhydrazones. Synthesis of Condensed Carbo- and Heterocycles by Formation of a C-C Single Bond and a C=C Double Bond on the Same Carbon Atom. Org. Lett. 2017, 19, 2034. (6) (a) Zhou, L.; Ye, F.; Zhang, Y.; Wang, J. Pd-Catalyzed ThreeComponent Coupling of N-Tosylhydrazone, Terminal Alkyne, and Aryl Halide. J. Am. Chem. Soc. 2010, 132, 13590. (b) Xia, Y.; Hu, F.; Liu, Z.; Qu, P.; Ge, R.; Ma, C.; Zhang, Y.; Wang, J. Palladium-Catalyzed Diarylmethyl C(sp3)-C(sp2) Bond Formation: A New Coupling Approach toward Triarylmethanes. Org. Lett. 2013, 15, 1784. (c) Gutman, E. S.; Arredondo, V.; Van Vranken, D. L. Cyclization of η3Benzylpalladium Intermediates Derived from Carbene Insertion. Org. Lett. 2014, 16, 5498. (d) Paraja, M.; Pérez-Aguilar, M. C.; Valdés, C. The Pd-catalyzed Synthesis of Benzofused Carbo- and Heterocycles through Carbene Migratory Insertion/Carbopalladation Cascades with Tosylhydrazones. Chem. Commun. 2015, 51, 16241. (e) Arunprasath, D.; Muthupandi, P.; Sekar, G. Palladium-Catalyzed Intermolecular Carbene Insertion Prior to Intramolecular Heck Cyclization: Synthesis of 2Arylidene-3-aryl-1-indanones. Org. Lett. 2015, 17, 5448. (f) Paraja, M.; 4768

DOI: 10.1021/acs.joc.8b00615 J. Org. Chem. 2018, 83, 4762−4768