FULL PAPER

DOI: 10.1002/ejoc.201402938

Ruthenium-Catalyzed Alkenylation of Arenes with Alkynes or Alkenes by1,2,3-Triazole-Directed C–H Activation

Xing Guang Li,[a] Kai Liu,[a] Gang Zou,[a] and Pei Nian Liu*[a]

Keywords: Synthetic methods / Alkenylation / C–H activation / Ruthenium / Alkynes / Alkenes

The ruthenium-catalyzed alkenylation of arenes with alk-ynes or alkenes has been achieved by using 1,2,3-triazole asthe directing group for the C–H activation. With [Ru(p-cymene)Cl2]2 as the catalyst and Cu(OAc)2·H2O and AgSbF6

Introduction

Transition-metal-catalyzed C–H-activated alkenylationof arenes with alkynes is an alternative to the traditionalHeck coupling reaction for the construction of new C–Cbonds that is atom economic and efficient without prefunc-tionalized reagents.[1] In 1986, Lewis and Smith reported oncatalytic C–C bond formation via ortho-metalated com-plexes.[2] After the pioneering work by Kakiuchi and Trostand their co-workers using [RuH2(CO)(PPh3)3] as cata-lyst,[3] ruthenium,[4] rhodium,[5] palladium,[6] iridium,[7] rhe-nium,[8] nickel,[9] and cobalt[10] have been successfully ap-plied as efficient catalysts in the C–H-activated alkenylationof arenes with alkynes.

The chelation-assisted C–H activation approach hasemerged as a powerful strategy for the cleavage and func-tionalization of inert C–H bonds and attracted considerableinterest in recent years.[11] Triazene,[12] nitroso,[13] sulfox-imine,[14] P=O bonds,[15] and unsaturated C–C bonds[16]

have been explored as effective directing groups (DG) toassist selective C–H bond functionalization and employedin a variety of reactions.

Since the discovery of the CuI-catalyzed 1,3-dipolar cy-cloaddition of azides and alkynes to afford 1,2,3-triazole in2002,[17] a wide range of applications of this click reactionhave been described, especially in the areas of organic syn-thesis, chemical biology, drug development, and materialssciences.[18] Owing to the increasing importance of the1,2,3-triazole scaffold that results from click chemistry and

[a] Shanghai Key Laboratory of Functional Materials Chemistry,Key Laboratory for Advanced Materials and Institute of FineChemicals, East China University of Science and Technology,Shanghai, 200237, P. R. ChinaE-mail: liupn@ecust.edu.cnhttp://hyxy.ecust.edu.cn/new/viewProf.php?id=371Supporting information for this article is available on theWWW under http://dx.doi.org/10.1002/ejoc.201402938.

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as additives, various triazole-substituted arenes reactedreadily with a range of internal alkynes or terminal alkenesto afford di- or monoalkenylated arenes with high regioselec-tivity and in moderate-to-excellent yields.

the biological activities of the molecules in which it is aconstituent,[18,19] we intended to take advantage of the1,2,3-triazole moiety as a directing group in transition-metal-catalyzed C–H bond activation reactions. Althoughexamples of C–H functionalization by employing 1,2,3-tri-azoles as directing groups have already been reported byAckermann and co-workers,[20] this interesting area is wor-thy of further exploration.

Recently, we reported the ruthenium-catalyzed click reac-tion of azides and alkynes to produce 1,2,3-triazole.[21] Inthis report we demonstrate the ruthenium-catalyzed C–H-activated alkenylation of arenes with internal alkynes andalkenes by using 1,2,3-triazole as the directing group.

Results and Discussion

In the first stage, 1-benzyl-4-phenyl-1H-1,2,3-triazole(1a, 0.2 mmol) and 1,2-diphenylethyne (2a, 0.5 mmol) wereselected as model substrates and [Ru(p-cymene)Cl2]2(0.01 mmol, 5 mol-%) was used as the catalyst to optimizethe reaction conditions (Table 1). In the presence ofAgSbF6 (20 mol-%) and Cu(OAc)2·H2O (1.2 equiv.) in o-xylene at 100 °C under nitrogen for 2.5 h, the reaction pro-vided the dialkenylated product 3a in 73% isolated yieldwith high regio- and stereoselectivity, as confirmed byNOESY spectroscopy (entry 1). Screening of the solventsrevealed that toluene is the best solvent to produce product3a in 93 % yield; CH2Cl2 and tert-amyl alcohol gave yieldsof 88 and 29%, whereas CH3CN, DMF, and THF were noteffective in this transformation (entries 2–7). The control re-action did not proceed without [Ru(p-cymene)Cl2]2 orCu(OAc)2·H2O, which confirms that they are necessary inthe catalytic cycle (entries 8 and 9). Moreover, the absenceof AgSbF6 from the reaction gave product 3a in only traceamounts (8% yield), which illustrates that the dehalogena-

Ruthenium-Catalyzed Alkenylation of Arenes

tion of [Ru(p-cymene)Cl2]2 by AgSbF6 is essential for theinitiation of the catalytic reaction (entry 10). Comparedwith the result of entry 7, decreasing the amount ofCu(OAc)2·H2O to 0.2 equiv. resulted in no significantchange in yield (entry 11). When NaOAc was used insteadof Cu(OAc)2·H2O, 89% yield of product 3a was provided(entry 12). While other acetate additives like KOAc andCsOAc were found to be less effective or even ineffective inthis dialkenylation reaction (entries 13 and 14). Finally, westudied the effect of reaction temperature and found thatthe product yield decreased significantly to 23 % when low-ering the temperature to 80 °C (entry 15), whereas no prod-uct was obtained at 60 °C. In addition, the reaction of 1awith the same equivalents of the alkyne 2a (0.2 mmol) wasalso conducted. Interestingly, 3a was isolated as the onlyproduct in 40% yield with the recovery of 41% of 1a (en-try 16).

Table 1. Optimization of the reaction conditions.[a]

Entry Additive [equiv.] Solvent Yield [%][b]

1 Cu(OAc)2·H2O (1.2) o-xylene 77 (73)[c]2 Cu(OAc)2·H2O (1.2) CH3CN 03 Cu(OAc)2·H2O (1.2) DMF 64 Cu(OAc)2·H2O (1.2) THF 65 Cu(OAc)2·H2O (1.2) tAmOH 296 Cu(OAc)2·H2O (1.2) DCM 887 Cu(OAc)2·H2O (1.2) toluene 938[d] Cu(OAc)2·H2O (1.2) toluene n.r.9 – toluene n.r.10[e] Cu(OAc)2·H2O (1.2) toluene 811 Cu(OAc)2·H2O (0.2) toluene 9412 NaOAc (0.2) toluene 8913 KOAc (0.2) toluene 714 CsOAc (0.2) toluene trace15[f] Cu(OAc)2·H2O (0.2) toluene 2316[g] Cu(OAc)2·H2O (0.2) toluene 40

[a] Reaction conditions (unless otherwise noted): 1a (0.20 mmol),2a (0.50 mmol), AgSbF6 (0.04 mmol), [Ru(p-cymene)Cl2]2(0.01 mmol), additive, solvent (1.5 mL), 100 °C, Ar, 2.5 h. [b] Yieldbased on 1a, determined by 1H NMR integration using PhSiMe3as the internal standard; n.r.: no reaction. [c] The yield in parenthe-ses is the isolated yield. [d] Without [Ru(p-cymene)Cl2]2. [e] With-out AgSbF6. [f] At 80 °C. [g] 0.20 mmol 2a was used.

To determine the scope of the triazole-directed C–H-acti-vated alkenylation, a series of triazole-substituted areneswere employed in the reaction with various internal alkynesat 100 °C in toluene with [Ru(p-cymene)Cl2]2 (5 mol-%) asthe catalyst and Cu(OAc)2·H2O (20 mol-%) and AgSbF6(20 mol-%) as additives (Table 2). The reaction of 2a withtriazole-substituted benzenes bearing an electron-donatingmethyl or electron-withdrawing F, Cl, CF3, or NO2 group atthe para position provided the corresponding dialkenylated

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products 3b–3f in yields of 71–91 %. When the triazole-sub-stituted benzenes carried a methyl, methoxy, or chloro atthe ortho position, the alkenylation gave the monoalkenyl-ated products 3g–3i in yields of 64–72%. Moreover, if Me,F, or Cl was present at the meta position, then the corre-sponding dialkenylated products 3j–3l could also be ob-tained in moderate-to-good yields. If the benzyl substituentof the triazole moiety carried a methyl, methoxy, or fluorogroup at the para position, the arenes reacted smoothly with2a to afford the products 3m–3o in yields of 78–82%. Thereactions of 1 and 2a proceeded smoothly on changing thebenzyl substituent on N1 in the triazole moiety of 1a to 1-phenylethyl, 2-phenylpropanyl, dodecyl, or cyclohexyl togive the corresponding products 3p–3s in moderate yieldsof 70–76 %.

Subsequently, the scope of internal alkynes was also ex-amined in this alkenylation reaction. Internal diarylalkynesbearing electron-withdrawing Cl and CF3 substituents atthe para position of the phenyl ring showed good reactivityin the reaction with 1a, and the products 3v and 3w weregenerated in yields of 77 and 83%, respectively. However,when diarylalkynes bearing electron-donating Me or OMegroups were used as substrates in the reaction with 1a,lower yields of 63 and 52% were obtained. The reactionsof unsymmetrical internal alkynes, namely phenylacetylenessubstituted with a methyl or n-hexyl group, with 1a pro-ceeded smoothly to afford the products 3x and 3y as theonly isomers in yields of 61 and 74 % with high regioselec-tivity. However, the reactions of terminal alkynes such as1-octyne and phenylacetylene did not produce the desiredproducts.

To obtain some mechanistic insight into the ruthenium-catalyzed triazole-directed C–H-activated alkenylation ofarenes with alkynes, competition and deuteriation experi-ments were performed (Scheme 1). The substrate 1i wastreated with 1,2-diphenylacetylene (2a, 2.5 equiv.) and 1-phenyl-1-octyne (2g, 2.5 equiv.), and product 3i was ob-tained in 55 % yield in comparison with a 19% yield ofproduct 3z, which suggests that the reactivity of diarylalk-yne is superior to that of alkyl(phenyl)acetylene in this alk-enylation reaction [Scheme 1, Equation (1)]. When 1a alonewas treated with D2O [20 equiv., Cu(OAc)2 was used in-stead of Cu(OAc)2·H2O] under the standard reaction condi-tions for 60 min, 93% D of deuteriated 1a-d1-2 was ob-served [Equation (2)], which indicates that the formation ofthe ruthenacycle B by C–H cleavage is reversible. Next, 1a-d5 was treated with 2a (2.5 equiv.) under the standard con-ditions for 2.5 h, which afforded the product in 88% yieldwith 77% deuterium in the olefin [Equation (3)]. Next, anintermolecular competition reaction between 1a and 1a-d5with 2a was investigated and an apparent KIE of 2.0 wasobserved [Equation (4)]. Moreover, two parallel reactions of1a and 1a-d5 with 2a were also performed and showed asimilar KIE value of 2.6 (see the Supporting Information).Together, these facts indicate that C–H cleavage might beinvolved in the rate-determining step.

On the basis of above experiments and the knownmechanism of the directing-group-assisted C–H alkenyl-

X. G. Li, K. Liu, G. Zou, P. N. LiuFULL PAPERTable 2. Alkenylation of triazole-substituted arenes with internal alkynes.[a,b]

[a] Reaction conditions: 1 (0.20 mmol), alkyne 2 (0.50 mmol), [Ru(p-cymene)Cl2]2 (0.01 mmol), Cu(OAc)2·H2O (0.04 mmol), AgSbF6(0.04 mmol), toluene (1.5 mL), 100 °C, Ar, 2.5 h. [b] Isolated yields.

ation catalyzed by transition metals, a plausible mechanismfor the current reaction is illustrated in Scheme 2. AgSbF6functions as a chloride abstractor with the assistance ofCu(OAc)2·H2O to remove the chloride ligands from thecomplex [Ru(p-cymene)Cl2]2 and generate the cationic com-plex A. After coordination of triazole nitrogen to the RuII

complex, reversible cyclometalation through a carboxylate-assisted deprotonation[11j] gives ruthenacycle B. Insertion ofthe alkyne into the Ru–C bond of complex B providesseven-membered ruthenacycle C, which forms the singlealkenylated product D by protonation. The alkenylated

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arene D might be much more reactive than arene 1 underthe catalytic conditions because D could not be isolatedfrom the reaction. A similar process from D to F and subse-quent protonation by acetic acid afford the final dialkenyl-ated product 3 and regenerate the reactive species A.

On the other hand, the transition-metal-catalyzed oxidat-ive alkenylation of arenes with alkenes has also been viewedas an environmentally benign strategy.[22] Compared withthe traditional Mizoroki–Heck reaction,[23] this direct alk-enylation by C–H activation not only simplifies the experi-mental procedure, but also minimizes the amount of by-

Ruthenium-Catalyzed Alkenylation of Arenes

Scheme 1. Competition and deuteriation experiments.

product produced in the reaction. After the important workof Moritani and Fujiwara,[24] the palladium-[25] and rho-dium-catalyzed[26] oxidative alkenylation reactions of areneswith alkenes have been exploited and attracted considerableattention. The ruthenium catalysts have also proven to beeffective in this significant transformation.[27] Then we ex-plored the oxidative alkenylation of triazole-substitutedarenes with alkenes by using [Ru(p-cymene)Cl2]2 as the cat-alyst. The amount of Cu(OAc)2·H2O was increased to2.2 equiv., acting as an oxidant in this transformation. Un-der the typical reaction conditions indicated in Table 3,various acrylates (entries 1–5) were effectively coupled with

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triazolyl-substituted toluene 1b [1-benzyl-4-(o-tolyl)-1H-1,2,3-triazole] to form the products 5a–5e only as E stereo-isomers in yields of 65–70 %. When styrene and its deriva-tives with Me, OMe, F, or Cl at the para position weretreated with 1b, moderate-to-good yields (53–81%) of theproducts 5f–5j were obtained (entries 6–10). Unfortunately,disubstituted alkenes such as cyclohexene, methyl methac-rylate, and 2-chloroacrylonitrile were not suitable for thereaction. If R1 in triazolyl-substituted 1 was changed fromMe to OMe or Cl, the alkenylation with ethyl acrylate alsoproceeded to generate the corresponding products 5k and5l in yields of 51 and 62%, respectively (entries 11 and 12).

X. G. Li, K. Liu, G. Zou, P. N. LiuFULL PAPER

Scheme 2. Competition and deuteriation experiments.

(5)

Table 3. Alkenylation of 1,2,3-triazoles with different terminal alkenes.[a]

Entry R1 R2 Time [h] Product Yield [%][b]

1 Me CO2Me 2.5 5a 702 Me CO2Et 2.5 5b 713 Me CO2Bu 2.5 5c 664 Me CO2Cy 1 5d 655 Me CO2tBu 2.5 5e 696 Me Ph 5 5f 607 Me 4-MeC6H4 7 5g 588 Me 4-OMeC6H4 12 5h 539 Me 4-FC6H4 5 5i 6310 Me 4-ClC6H4 5 5j 8111 OMe CO2Et 1 5k 5112 Cl CO2Et 1 5l 62

[a] Reaction conditions: 1 (0.20 mmol), 4 (0.50 mmol), [Ru(p-cymene)Cl2]2 (0.01 mmol), Cu(OAc)2·H2O (0.44 mmol), AgSbF6(0.04 mmol), DCE (1.5 mL), 100 °C, Ar. [b] Isolated yields.

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However, in the reaction of 1a with methyl acrylate (4a)under the typical conditions, a mixture of mono- (5m) anddialkenylated (5m�) products was predominantly obtained,see Equation (5).

Conclusions

We have developed a ruthenium-catalyzed alkenylationof arenes with alkynes or alkenes through triazole-directedC–H activation. Various mono- and dialkenylated productswere regioselectively obtained in moderate-to-good yieldswith Cu(OAc)2·H2O and AgSbF6 as additives. As a resultof the comprehensive application of triazole-substituted ar-enes in click chemistry, the protocols described in this workmay provide straightforward methods for the derivation ofdiazole-substituted arenes that may be applied to materialsor pharmaceutical chemistry.

Experimental SectionGeneral Method: All manipulations were carried out under nitrogenby using standard Schlenk techniques unless otherwise stated. Sol-vents were distilled and dried under nitrogen. 1,2,3-Triazoles[21a]

Ruthenium-Catalyzed Alkenylation of Arenes

and 1,2-diphenylethynes[26d] were prepared according to literaturemethods. Chemical shifts (δ, ppm) in the 1H NMR spectra weredetermined by using TMS as internal standard. Chemical shiftsin 13C{1H} NMR spectra are internally referenced to CHCl3 (δ =77.16 ppm). The 1H chemical shift of water is 1.54–1.56 ppm.HRMS were recorded with an EI-TOF or ESI-TOF mass spec-trometer.

General Procedure for the Alkenylation of 1,2,3-Triazole with In-ternal Alkynes � General Procedure A: A mixture of 1,2,3-triazole(0.20 mmol), alkyne (0.50 mmol), Cu(OAc)2·H2O (0.04 mmol),AgSbF6 (0.04 mmol), [Ru(p-cymene)Cl2]2 (0.01 mmol), and toluene(1.5 mL) was stirred at 100 °C in a sealed tube under nitrogen for2.5 h. After cooling to ambient temperature, the product 3 was iso-lated by column chromatography on silica gel using petroleum/ethylacetate as eluent.

General Procedure for the Alkenylation of 1,2,3-Triazole with Ter-minal Alkenes � General Procedure B: A mixture of 1,2,3-triazole(0.20 mmol), alkene (0.50 mmol), Cu(OAc)2·H2O (0.44 mmol),AgSbF6 (0.04 mmol), [Ru(p-cymene)Cl2]2 (0.01 mmol), and DCE(1.5 mL) was stirred at 100 °C in a sealed tube under nitrogen forseveral hours. After cooling to ambient temperature, the product 5was isolated by column chromatography on silica gel using petro-leum/ethyl acetate as eluent.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]phenyl}-1H-1,2,3-triazole(3a): The title compound was isolated by column chromatography(petroleum/ethyl acetate = 10:1) as a light-yellow viscous liquid(106 mg, 90% yield) from 1-benzyl-4-phenyl-1H-1,2,3-triazole (1a)according to General Procedure A. 1H NMR (400 MHz, CDCl3):δ = 5.04 (s, 2 H), 6.19 (s, 1 H), 6.58 (s, 2 H), 6.78 (d, J = 7.4 Hz,4 H), 6.88 (d, J = 7.5 Hz, 2 H), 6.92–6.97 (m, 8 H), 7.02–7.08 (m, 10H), 7.16–7.19 (m, 1 H), 7.41 (s, 3 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 53.5, 123.0, 126.7, 126.8, 127.8, 128.0, 128.36, 128.41,128.9, 129.4, 129.8, 131.3, 134.6, 137.3, 140.7, 142.2, 145.5,146.2 ppm. HRMS (EI, TOF): calcd. for C43H33N3 [M]+ 591.2674;found 591.2672.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]-4-methylphenyl}-1H-1,2,3-triazole (3b): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (110 mg, 91% yield) from 1-benzyl-4-(p-tolyl)-1H-1,2,3-triazole (1b) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 2.41 (s, 3 H), 5.04 (s, 2 H), 6.18 (s, 1 H),6.56 (s, 2 H), 6.79 (d, J = 7.4 Hz, 4 H), 6.86 (d, J = 7.5 Hz, 2 H),6.94–6.98 (m, 8 H), 7.02–7.08 (m, 10 H), 7.15–7.19 (m, 1 H), 7.22(s, 2 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.3, 53.5, 123.1,126.6, 126.7, 127.8, 127.9, 128.3, 128.8, 129.4, 129.7, 130.0, 130.5,134.5, 137.3, 138.1, 140.6, 142.2, 145.5, 146.0 ppm. HRMS (EI,TOF): calcd. for C44H35N3 [M]+ 605.2831; found 605.2830.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]-4-fluorophenyl}-1H-1,2,3-triazole (3c): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (86 mg, 71 % yield) from 1-benzyl-4-(4-fluoro-phenyl)-1H-1,2,3-triazole (1c) according to General Procedure A.1H NMR (400 MHz, CDCl3): δ = 5.04 (s, 2 H), 6.17 (s, 1 H), 6.58(s, 2 H), 6.77 (d, J = 7.2 Hz, 4 H), 6.86 (d, J = 7.6 Hz, 2 H), 6.91–6.93 (m, 4 H), 6.97 (t, J = 8.8 Hz, 4 H), 7.02–7.09 (m, 1 H), 7.12 (s,1 H), 7.14 (s, 1 H), 7.15–7.19 (m, 1 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 53.5, 116.4 (d, J = 21.3 Hz), 123.1, 125.6 (d, J =2.9 Hz), 126.9, 127.0, 127.9, 127.96, 128.01, 128.4, 128.8, 129.4,129.7, 131.9, 134.5, 126.9, 140.1, 141.2, 144.7, 148.3 (d, J = 8.1 Hz),162.2 (d, J = 249.0 Hz) ppm. HRMS (EI, TOF): calcd. forC43H32N3F [M]+ 609.2580; found 609.2575.

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1-Benzyl-4-{4-chloro-2,6-bis[(E)-1,2-diphenylvinyl]phenyl}-1H-1,2,3-triazole (3d): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (105 mg, 84 % yield) from 1-benzyl-4-(4-chloro-phenyl)-1H-1,2,3-triazole (1d) according to General Procedure A.1H NMR (400 MHz, CDCl3): δ = 5.03 (s, 2 H), 6.17 (s, 1 H), 6.58(s, 2 H), 6.76 (d, J = 7.2 Hz, 4 H), 6.87 (d, J = 7.6 Hz, 2 H), 6.91–6.98 (m, 8 H), 7.03–7.09 (m, 10 H), 7.16–7.20 (m, 1 H), 7.42 (s, 2H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 53.5, 123.1, 126.9,127.0, 127.9, 127.95, 128.01, 128.1, 128.4, 128.9, 129.4, 129.5,129.7, 132.0, 134.2, 134.4, 136.9, 139.9, 141.0, 144.5, 147.7 ppm.HRMS (EI, TOF): calcd. for C43H32N3Cl [M]+ 625.2285; found625.2284.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]-4-(trifluoromethyl)-phenyl}-1H-1,2,3-triazole (3e): The title compound was isolated bycolumn chromatography (petroleum/ethyl acetate = 10:1) as a light-yellow viscous liquid (107 mg, 81% yield) from 1-benzyl-4-[4-(tri-fluoromethyl)phenyl]-1H-1,2,3-triazole (1e) according to GeneralProcedure A. 1H NMR (400 MHz, CDCl3): δ = 5.03 (s, 2 H), 6.17(s, 1 H), 6.62 (s, 2 H), 6.73 (d, J = 7.1 Hz, 4 H), 6.89–6.97 (m, 10H), 6.97 (t, J = 8.8 Hz, 4 H), 7.03–7.10 (m, 10 H), 7.12 (s, 1 H),7.18–7.22 (m, 1 H), 7.68 (s, 2 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 53.5, 123.0, 124.1 (q, J = 272.5 Hz), 126.3 (q, J =3.6 Hz), 127.0, 127.1, 127.9, 128.01, 128.03, 128.5, 128.9, 129.4,129.6, 130.6 (q, J = 32.4 Hz), 132.1, 133.2, 134.2, 136.7, 139.7,141.0, 144.2, 147.0 ppm. HRMS (EI, TOF): calcd. for C44H32N3F3[M]+ 659.2548; found 659.2549.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]-4-nitrophenyl}-1H-1,2,3-triazole (3f): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (104 mg, 82% yield) from 1-benzyl-4-(4-nitrophenyl)-1H-1,2,3-triazole (1f) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 5.05 (s, 2 H), 6.27 (s, 1 H), 6.65 (s, 2 H),6.74 (d, J = 7.1 Hz, 4 H), 6.90 (d, J = 7.3 Hz, 2 H), 6.93–6.99 (m,8 H), 7.05–7.12 (m, 10 H), 7.19–7.22 (m, 1 H), 8.28 (s, 2 H) ppm.13C NMR (100.6 MHz, CDCl3): δ = 53.7, 123.2, 124.1, 127.3,127.4, 128.08, 128.1, 128.6, 129.0, 129.4, 129.6, 132.9, 134.1, 136.2,136.5, 139.3, 140.2, 143.7, 147.6, 147.8 ppm. HRMS (EI, TOF):calcd. for C43H32N4O2 [M]+ 636.2525; found 636.2524.

(E)-1-Benzyl-4-[2-(1,2-diphenylvinyl)-6-methylphenyl]-1H-1,2,3-tri-azole (3g): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 10:1) as a light-yellow viscous li-quid (59 mg, 69 % yield) from 1-benzyl-4-(o-tolyl)-1H-1,2,3-triazole(1g) according to General Procedure A. 1H NMR (400 MHz,CDCl3): δ = 2.13 (s, 3 H), 5.34 (s, 2 H), 6.56 (s, 1 H), 6.74–6.76(m, 2 H), 6.90 (s, 1 H), 6.93–6.97 (m, 4 H), 7.02–7.12 (m, 6 H),7.19–7.31 (m, 6 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 20.9,53.9, 122.8, 126.7, 127.8, 128.0, 128.1, 128.5, 128.6, 129.1, 129.4,129.5, 129.6, 129.7, 130.9, 134.7, 137.3, 138.6, 140.5, 142.6, 145.7,145.8 ppm. HRMS (EI, TOF): calcd. for C30H25N3 [M]+ 427.2048;found 427.2047.

(E)-1-Benzyl-4-[2-(1,2-diphenylvinyl)-6-methoxyphenyl]-1H-1,2,3-tri-azole (3h): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 8:1) as a light-yellow viscous li-quid (57 mg, 64% yield) from 1-benzyl-4-(2-methoxyphenyl)-1H-1,2,3-triazole (1h) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 3.73 (s, 3 H), 5.36 (s, 2 H), 6.61 (s, 1 H),6.84–6.92 (m, 2 H), 6.91–7.10 (m, 13 H), 7.19–7.28 (m, 3 H), 7.33–7.37 (m, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 53.8, 56.0,110.1, 119.3, 123.3, 123.7, 126.67, 126.70, 127.7, 127.9, 128.1,128.5, 128.9, 129.39, 129.45, 129.9, 130.9, 134.9, 137.5, 140.4,

X. G. Li, K. Liu, G. Zou, P. N. LiuFULL PAPER142.3, 142.7, 146.8, 157.9 ppm. HRMS (EI, TOF): calcd. forC30H25N3O [M]+ 433.1998; found 433.1999.

(E)-1-Benzyl-4-[2-chloro-6-(1,2-diphenylvinyl)phenyl]-1H-1,2,3-tri-azole (3i): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 10:1) as a light-yellow viscous li-quid (69 mg, 72 % yield) from 1-benzyl-4-(2-chlorophenyl)-1H-1,2,3-triazole (1i) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 5.34 (s, 2 H), 6.63 (s, 1 H), 6.79 (d, J =7.1 Hz, 2 H), 6.92–6.98 (m, 5 H), 7.01–7.05 (m, 1 H), 7.07–7.11 (m,5 H), 7.21–7.25 (m, 2 H), 7.26–7.31 (m, 1 H), 7.34 (d, J = 7.7 Hz,1 H), 7.37–7.39 (m, 1 H), 7.41–7.43 (m, 1 H) ppm. 13C NMR(100.6 MHz, CDCl3): δ = 53.9, 123.6, 126.9, 127.0, 127.9, 128.0,128.1, 128.6, 128.7, 129.0, 129.2, 129.3, 129.5, 129.6, 129.8, 131.6,134.6, 135.2, 137.0, 140.1, 141.6, 143.8, 147.8 ppm. HRMS (EI,TOF): calcd. for C29H22N3Cl [M]+ 447.1502; found 447.1505.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]-3-methylphenyl}-1H-1,2,3-triazole (3j): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 8:1) as a light-yellowviscous liquid (66 mg, 55 % yield) from 1-benzyl-4-(m-tolyl)-1H-1,2,3-triazole (1j) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 2.30 (s, 3 H), 4.99 (d, J = 15.0 Hz, 1 H),5.14 (d, J = 14.9 Hz, 1 H), 6.29 (s, 1 H), 6.39 (s, 1 H), 6.68 (s, 1H), 6.81–6.86 (m, 6 H), 6.90–7.09 (m, 18 H), 7.14–7.18 (m, 1 H),7.28 (d, J = 7.8 Hz, 1 H), 7.37 (d, J = 7.9 Hz, 1 H) ppm. 13C NMR(100.6 MHz, CDCl3): δ = 20.7, 53.5, 123.3, 126.5, 126.6, 126.8,126.9, 127.7, 127.8, 127.9, 128.1, 128.3, 128.8, 129.2, 129.5, 129.8,129.9, 130.0, 130.5, 130.9, 131.6, 134.6, 136.2, 137.3, 137.6, 139.2,140.0, 141.1, 142.7, 143.9, 144.7, 145.9 ppm. HRMS (EI, TOF):calcd. for C44H35N3 [M]+ 605.2831; found 605.2833.

1-Benzyl-4-{2,6-bis[(E)-1,2-diphenylvinyl]-3-fluorophenyl}-1H-1,2,3-triazole (3k): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (97 mg, 80 % yield) from 1-benzyl-4-(3-fluo-rophenyl)-1H-1,2,3-triazole (1k) according to General ProcedureA. 1H NMR (400 MHz, CDCl3): δ = 5.10 (s, 2 H), 6.43 (s, 1 H),6.49 (s, 1 H), 6.64 (s, 1 H), 6.78–6.80 (m, 2 H), 6.82–6.91 (m, 6 H),6.95–7.09 (m, 17 H), 7.14–7.18 (m, 2 H), 7.41 (dd, J1 = 5.6, J2 =8.6 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 53.5, 115.8(d, J = 23.0 Hz), 126.7, 126.8, 127.0, 127.80, 127.83, 127.9, 128.0,128.4, 128.9, 129.3, 129.40, 129.42, 129.8, 130.9 (d, J = 8.4 Hz),131.4, 131.8 (d, J = 3.4 Hz), 133.0, 133.2, 133.4, 134.4, 134.5, 136.6,137.2, 137.2, 139.5, 140.6, 141.6, 142.2 (d, J = 3.6 Hz), 144.6 (d, J= 2.8 Hz), 159.6 (d, J = 246.0 Hz) ppm. HRMS (EI, TOF): calcd.for C43H32N3F [M]+ 609.2580; found 609.2582.

1-Benzyl-4-{3-chloro-2,6-bis[(E)-1,2-diphenylvinyl]phenyl}-1H-1,2,3-triazole (3l): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowv i s cou s l iq u id (94 mg, 75 % yie ld ) f rom 1-benzyl -4 - (3-chlorophenyl)-1H-1,2,3-triazole (1l) according to General Pro-cedure A. 1H NMR (400 MHz, CDCl3): δ = 5.02 (d, J = 15.1 Hz,1 H), 5.14 (d, J = 15.1 Hz, 1 H), 6.29 (s, 1 H), 6.47 (s, 1 H), 6.67(s, 1 H), 6.77–6.81 (m, 3 H), 6.88 (d, 2 H), 6.91–6.98 (m, 8 H),7.02–7.10 (m, 10 H), 7.17 (t, J = 7.4 Hz, 1 H), 7.40 (d, J = 8.3 Hz,1 H), 7.50 (d, J = 8.3 Hz, 1 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 53.6, 123.3, 126.7, 126.9, 127.0, 127.1, 127.79, 127.81,127.9, 128.0, 128.1, 128.5, 128.9, 129.3, 129.5, 129.7, 129.8, 129.9,130.6, 131.6, 131.9, 132.9, 133.6, 134.4, 136.8, 137.1, 138.1, 138.6,140.5, 141.6, 143.7, 144.9, 145.0 ppm. HRMS (ESI, TOF): calcd.for C29H31N3Cl [M + H]+ 626.2363; found 626.2360.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-(4-methylbenzyl)-1H-1,2,3-triazole (3m): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellow

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viscous liquid (97 mg, 80 % yield) from 1-(4-methylbenzyl)-4-phenyl-1H-1,2,3-triazole (1m) according to General Procedure A.1H NMR (400 MHz, CDCl3): δ = 2.23 (s, 3 H), 4.99 (s, 2 H), 6.18(s, 1 H), 6.57 (s, 2 H), 6.74–6.85 (m, 8 H), 6.91–6.98 (m, 8 H), 7.02–7.08 (m, 8 H), 7.40 (s, 3 H) ppm. 13C NMR (100.6 MHz, CDCl3):δ = 21.2, 53.3, 122.9, 126.67, 126.72, 127.8, 127.9, 128.0, 128.4,129.4, 129.5, 129.8, 131.2, 131.6, 137.3, 138.1, 140.6, 142.2, 145.4,146.2 ppm. HRMS (EI, TOF): calcd. for C44H35N3 [M]+ 605.2831;found 605.2830.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-(4-methoxybenzyl)-1H-1,2,3-triazole (3n): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (102 mg, 82 % yield) from 1-(4-methoxybenzyl)-4-phenyl-1H-1,2,3-triazole (1n) according to General Procedure A.1H NMR (400 MHz, CDCl3): δ = 3.70 (s, 3 H), 4.98 (s, 2 H), 6.18(s, 1 H), 6.53–6.57 (m, 4 H), 6.77–6.81 (m, 6 H), 6.92–6.99 (m, 8H), 7.03–7.08 (m, 8 H), 7.40 (s, 3 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 52.9, 55.4, 114.2, 122.8, 126.6, 126.67, 126.71, 127.8,127.9, 128.4, 129.4, 129.4, 129.5, 129.7, 129.8, 131.2, 137.4, 140.6,142.2, 145.4, 146.1, 159.6 ppm. HRMS (EI, TOF): calcd. forC44H35N3O [M]+ 621.2780; found 621.2778.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-(4-fluorobenzyl)-1H-1,2,3-triazole (3o): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (95 mg, 78 % yield) from 1-(4-fluorobenzyl)-4-phenyl-1H-1,2,3-triazole (1o) according to General Procedure A.1H NMR (400 MHz, CDCl3): δ = 5.01 (s, 2 H), 6.20 (s, 1 H), 6.56(s, 2 H), 6.67–6.71 (m, 2 H), 6.78–6.85 (m, 6 H), 6.90–6.93 (m, 4H), 6.96–7.00 (m, 4 H), 7.04–7.08 (m, 8 H), 7.40 (s, 3 H) ppm. 13CNMR (100.6 MHz, CDCl3): δ = 52.6, 115.8 (d, J = 21.9 Hz), 122.9,126.7, 126.8, 127.8, 128.0, 128.5, 129.3, 129.4, 129.6 (d, J = 8.5 Hz),129.8, 130.4 (d, J = 3.1 Hz), 131.3, 137.2, 140.7, 142.0, 145.7, 146.1,162.6 (d, J = 247.3 Hz) ppm. HRMS (EI, TOF): calcd. forC43H32N3F [M]+ 609.2580; found 609.2576.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-(1-phenylethyl)-1H-1,2,3-triazole (3p): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (91 mg, 75% yield) from 4-phenyl-1-(1-phenylethyl)-1H-1,2,3-triazole (1p) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 1.60 (d, J = 7.1 Hz, 3 H), 5.33 (q, J =7.1 Hz, 1 H), 6.36 (s, 1 H), 6.56 (s, 2 H), 6.78 (d, J = 7.6 Hz, 4 H),6.88–7.03 (m, 10 H), 7.06–7.08 (m, 6 H), 7.12–7.15 (m, 1 H), 7.39(s, 3 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.4, 59.7, 121.8,126.5, 126.7, 126.8, 127.8, 127.9, 128.2, 128.3, 128.7, 129.4, 129.5,129.7, 129.8, 131.2, 137.3, 139.9, 140.5, 142.2, 144.9, 146.0 ppm.HRMS (EI, TOF): calcd. for C44H35N3 [M]+ 605.2831; found605.2829.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-(2-phenylpropan-2-yl)-1H-1,2,3-triazole (3q): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (87 mg, 70 % yield) from 4-phenyl-1-(2-phenyl-propan-2-yl)-1H-1,2,3-triazole (1q) according to General ProcedureA. 1H NMR (400 MHz, CDCl3): δ = 1.68 (s, 6 H), 6.54 (s, 3 H),6.70 (d, J = 7.6 Hz, 2 H), 6.83–6.87 (m, 2 H), 6.92–6.96 (m, 8 H),7.03–7.12 (m, 13 H), 7.34–7.37 (m, 3 H) ppm. 13C NMR(100.6 MHz, CDCl3): δ = 29.8, 63.6, 121.9, 125.0, 126.8, 126.9,127.4, 128.0, 128.1, 128.4, 129.4, 129.8, 129.9, 131.5, 137.4, 140.6,142.0, 144.72, 144.75, 145.9 ppm. HRMS (EI, TOF): calcd. forC45H37N3 [M]+ 619.2987; found 619.2985.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-dodecyl-1H-1,2,3-triazole(3r): The title compound was isolated by column chromatography(petroleum/ethyl acetate = 10:1) as a light-yellow viscous liquid

Ruthenium-Catalyzed Alkenylation of Arenes

(102 mg, 76% yield) from 1-dodecyl-4-phenyl-1H-1,2,3-triazole (1r)according to General Procedure A. 1H NMR (400 MHz, CDCl3):δ = 0.88 (t, J = 6.9 Hz, 3 H), 1.03–1.10 (m, 6 H), 1.20–1.30 (m, 12H), 1.40–1.48 (m, 2 H), 3.81 (t, J = 7.5 Hz, 2 H), 6.17 (s, 2 H), 6.62(s, 1 H), 6.81–6.83 (m, 4 H), 6.95–6.98 (m, 4 H), 6.99–7.07 (m, 12H), 7.42–7.44 (m, 3 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ =14.2, 22.8, 26.5, 29.0, 29.4, 29.5, 29.6, 29.7, 30.2, 32.0, 49.6, 122.6,126.67, 126.74, 127.8, 127.9, 128.4, 129.4, 129.8, 129.9, 131.2,137.3, 140.7, 142.3, 145.0, 146.2 ppm. HRMS (EI, TOF): calcd. forC48H51N3 [M]+ 669.4083; found 669.4084.

4-{2,6-Bis[(E)-1,2-diphenylvinyl]phenyl}-1-cyclohexyl-1H-1,2,3-tri-azole (3s): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 10:1) as a light-yellow viscous li-quid (83 mg, 71 % yield) from 1-cyclohexyl-4-phenyl-1H-1,2,3-tri-azole (1s) according to General Procedure A. 1H NMR (400 MHz,CDCl3): δ = 1.21–1.26 (m, 4 H), 1.60–1.73 (m, 6 H), 3.94–3.97 (m,1 H), 6.28 (s, 1 H), 6.63 (s, 2 H), 6.79–6.81 (m, 4 H), 6.96–7.07 (m,15 H), 7.17–7.19 (m, 1 H), 7.44 (s, 3 H) ppm. 1 3 C NMR(100.6 MHz, CDCl3): δ = 25.1, 33.3, 59.4, 120.4, 126.7, 127.8,127.9, 128.3, 128.4, 129.7, 129.99, 130.04, 131.1, 137.4, 140.6,142.4, 144.4, 146.1 ppm. HRMS (EI, TOF): calcd. for C42H37N3[M]+ 583.2987; found 583.2991.

1-Benzyl-4-{2,6-bis[(E)-1,2-di-p-tolylvinyl]phenyl}-1H-1,2,3-triazole(3t): The title compound was isolated by column chromatography(petroleum/ethyl acetate = 10:1) as a light-yellow viscous liquid(82 mg, 63% yield) from 1,2-di-p-tolylethyne (2b) according to Ge-neral Procedure A. 1H NMR (400 MHz, CDCl3): δ = 2.25 (s, 12H), 5.06 (s, 2 H), 6.28 (s, 1 H), 6.47 (s, 2 H), 6.69–6.71 (m, 4 H),6.78–6.89 (m, 15 H), 7.02–7.06 (m, 2 H), 7.16–7.20 (m, 1 H), 7.34–7.35 (m, 3 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.3, 21.4,53.4, 123.1, 127.8, 128.20, 128.23, 128.5, 128.6, 128.8, 129.2, 129.3,129.5, 129.6, 130.8, 134.60, 134.64, 136.2, 136.3, 137.9, 141.2,145.6, 146.4 ppm. HRMS (EI, TOF): calcd. for C47H41N3 [M]+

647.3300; found 647.3302.

1-Benzyl-4-{2,6-bis[(E)-1,2-bis(4-methoxyphenyl)vinyl]phenyl}-1H-1,2,3-triazole (3u): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (74 mg, 52% yield) from 1,2-bis(4-methoxyphenyl)-ethyne (2c) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 3.73 (s, 6 H), 3.74 (s, 6 H), 5.08 (s, 2 H),6.30 (s, 1 H), 6.44 (s, 2 H), 6.54 (d, J = 8.8 Hz, 4 H), 6.54 (d, J =8.8 Hz, 4 H), 6.63 (d, J = 8.8 Hz, 4 H), 6.72 (d, J = 8.8 Hz, 4 H),6.86–6.90 (m, 6 H), 7.06–7.09 (m, 2 H), 7.19 (t, J = 7.4 Hz, 1 H),7.34–7.36 (m, 3 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 53.4,55.2, 55.2, 113.2, 113.3, 122.9, 127.9, 128.2, 128.3, 128.76, 128.80,129.3, 129.5, 130.0, 130.2, 130.5, 130.9, 133.3, 134.5, 140.0, 145.6,146.4, 158.2 ppm. HRMS (ESI, TOF): calcd. for C47H42N3O4 [M+ H]+ 712.3175; found 712.3185.

1-Benzyl-4-{2,6-bis[(E)-1,2-bis(4-chlorophenyl)vinyl]phenyl}-1H-1,2,3-triazole (3v): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 10:1) as a light-yellowviscous liquid (112 mg, 77 % yield) from 1,2-bis(4-chlorophenyl)ethyne (2d) according to General Procedure A. 1H NMR(400 MHz, CDCl3): δ = 5.09 (s, 2 H), 6.27 (s, 1 H), 6.53 (s, 2 H),6.63 (d, J = 8.4 Hz, 4 H), 6.82 (d, J = 8.5 Hz, 4 H), 6.93 (d, J =8.5 Hz, 4 H), 6.98 (d, J = 7.4 Hz, 2 H), 7.06 (d, J = 8.5 Hz, 4 H),7.13–7.17 (m, 2 H), 7.24–7.28 (s, 1 H), 7.38–7.44 (m, 3 H) ppm.13C NMR (100.6 MHz, CDCl3): δ = 53.8, 122.9, 128.3, 128.4,128.8, 128.8, 129.1, 129.3, 130.1, 130.5, 130.6, 131.0, 132.8, 132.9,134.2, 135.3, 138.5, 141.6, 145.1, 145.4 ppm. HRMS (EI, TOF):calcd. for C43H29N3Cl4 [M]+ 727.1116; found 727.1120.

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1-Benzyl-4-(2,6-bis{(E)-1,2-bis[4-(trifluoromethyl)phenyl]-vinyl}phenyl)-1H-1,2,3-triazole (3w): The title compound was iso-lated by column chromatography (petroleum/ethyl acetate = 10:1)as a light-yellow viscous liquid (143 mg, 83% yield) from 1,2-bis[4-(trifluoromethyl)phenyl]ethyne (2e) according to General Pro-cedure A. 1H NMR (400 MHz, CDCl3): δ = 5.02 (s, 2 H), 6.31 (s,1 H), 6.69 (s, 2 H), 6.79 (d, J = 8.1 Hz, 4 H), 6.93–6.98 (m, 6 H),7.06 (t, J = 7.5 Hz, 2 H), 7.17–7.23 (m, 5 H), 7.35 (d, J = 8.2 Hz,2 H), 7.45–7.52 (m, 3 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ= 53.7, 122.7, 124.1 (q, J = 271.5 Hz), 124.1 (q, J = 272.0 Hz),125.0 (q, J = 3.7 Hz), 125.2 (q, J = 3.7 Hz), 128.1, 128.7, 128.8,128.9, 128.97, 129.03, 129.1, 129.3, 129.4, 129.5, 129.7, 130.0,130.4, 131.2, 134.1, 140.0, 142.9, 143.4, 145.0, 145.1 ppm. HRMS(ESI, TOF): calcd. for C47H30N3F12 [M + H]+ 864.2248; found864.2245.

1-Benzyl-4-{2,6-bis[(E)-1-phenylprop-1-en-2-yl]phenyl}-1H-1,2,3-tri-azole (3x): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 10:1) as a white solid (57 mg, 61%yield) from prop-1-yn-1-ylbenzene (2f) according to General Pro-cedure A, m.p. 174–176 °C. 1H NMR (400 MHz, CDCl3): δ = 1.88(s, 6 H), 5.5 (s, 2 H), 6.3 (s, 2 H), 7.04–7.14 (m, 8 H), 7.19–7.24(m, 3 H), 7.28–7.32 (m, 6 H), 7.36–7.40 (m, 2 H) ppm. 13C NMR(100.6 MHz, CDCl3): δ = 20.4, 54.0, 123.5, 126.5, 126.8, 127.4,127.5, 128.3, 128.5, 128.9, 129.0, 130.1, 135.3, 138.0, 139.4, 146.4,147.0 ppm. HRMS (EI, TOF): calcd. for C33H29N3 [M]+ 467.2361;found 467.2363.

1-Benzyl-4-{2,6-bis[(E)-1-phenyloct-1-en-2-yl]phenyl}-1H-1,2,3-tri-azole (3y): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 10:1) as a light-yellow viscous li-quid (90 mg, 74% yield) from oct-1-yn-1-ylbenzene (2g) accordingto General Procedure A. 1H NMR (400 MHz, CDCl3): δ = 0.80 (t,J = 7.1 Hz, 6 H), 1.08–1.09 (m, 8 H), 1.14–1.25 (m, 8 H), 2.07–2.11 (m, 4 H), 5.51 (s, 2 H), 6.37 (s, 2 H), 7.08–7.17 (m, 8 H), 7.19–7.31 (m, 9 H), 7.33–7.37 (m, 2 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 14.2, 22.7, 28.2, 29.4, 31.6, 32.2, 54.0, 123.6, 126.4,127.2, 127.6, 127.9, 128.2, 128.6, 128.8, 129.1, 130.3, 135.3, 138.1,144.5, 145.2, 146.2 ppm. HRMS (EI, TOF): calcd. for C43H49N3[M]+ 607.3926; found 607.3921.

Competition Experiment for Substrates 2a and 2g with 1i � Synthe-sis of (E)-1-Benzyl-4-[2-chloro-6-(1-phenyloct-1-en-2-yl)phenyl]-1H-1,2,3-triazole (3z): A mixture of 1,2,3-triazole 1i (0.20 mmol), alk-ynes 2a (0.50 mmol) and 2g (0.50 mmol), Cu(OAc)2 ·H2O(0.04 mmol) , AgSbF 6 (0 .04 mmol) , [Ru(p -cymene)Cl 2 ]2(0.01 mmol), and toluene (1.5 mL) was stirred at 100 °C in a sealedtube under nitrogen for 2.5 h. After cooling to ambient tempera-ture, the products 3i (49 mg, 55% yield) and 3z (17 mg, 19% yield)were isolated separately by column chromatography (petroleum/ethyl acetate = 10:1) as light-yellow oil. 1H NMR (400 MHz,CDCl3): δ = 0.79 (t, J = 7.3 Hz, 3 H), 1.04–1.18 (m, 8 H), 2.02 (t,J = 8.2 Hz, 2 H), 5.58 (s, 2 H), 6.29 (s, 1 H), 7.00 (d, J = 7.2 Hz,1 H), 7.16–7.25 (m, 6 H), 7.28–7.32 (m, 4 H), 7.41–7.44 (m, 1 H),7.44 (s, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 14.1, 22.7,28.1, 29.3, 31.5, 31.9, 54.2, 123.9, 126.7, 127.7, 127.8, 128.3, 128.4,128.7, 129.2, 129.5, 130.0, 134.99, 135.04, 137.5, 143.3, 144.2,147.2 ppm. HRMS (ESI, TOF): calcd. for C29H31N3Cl [M + H]+

456.2207; found 456.2212.

Methyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-methylphenyl]-acrylate (5a): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a white solid(47 mg, 70% yield) from methyl acrylate (4a) according to GeneralProcedure B, m.p. 132.1–133.8 °C. 1H NMR (400 MHz, CDCl3): δ= 2.19 (s, 3 H), 3.72 (s, 3 H), 5.66 (s, 2 H), 6.28 (d, J = 15.9 Hz, 1

X. G. Li, K. Liu, G. Zou, P. N. LiuFULL PAPERH), 7.29–7.34 (m, 4 H), 7.37–7.44 (m, 4 H), 7.48 (d, J = 15.8 Hz,1 H), 7.50–7.52 (m, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ= 20.9, 51.7, 54.3, 119.5, 123.8, 124.2, 127.9, 128.8, 128.9, 129.3,130.8, 131.9, 134.88, 134.89, 138.9, 143.6, 144.5, 167.2 ppm.HRMS (ESI, TOF): calcd. for C20H19N3O2 [M + H]+ 334.1556;found 334.1561.

Ethyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-methylphenyl]-acrylate (5b): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a white solid(49 mg, 71% yield) from ethyl acrylate (4b) according to GeneralProcedure B, m.p. 127.5–129.6 °C. 1H NMR (400 MHz, CDCl3): δ= 1.27 (t, J = 7.0 Hz, 3 H), 2.19 (s, 1 H), 4.18 (q, J = 7.1 Hz, 2 H),5.65 (s, 2 H), 6.28 (d, J = 15.9 Hz, 1 H), 7.30–7.33 (m, 4 H), 7.36–7.43 (m, 4 H), 7.48 (d, J = 16.1 Hz, 1 H), 7.50–7.52 (m, 1 H) ppm.13C NMR (100.6 MHz, CDCl3): δ = 14.4, 20.9, 54.3, 60.5, 119.9,123.8, 124.2, 127.9, 128.8, 128.9, 129.3, 130.8, 131.8, 134.8, 135.0,138.8, 143.3, 144.5, 166.7 ppm. HRMS (ESI, TOF): calcd. forC21H21N3O2 [M + H]+ 348.1712; found 348.1706.

Butyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-methylphenyl]-acrylate (5c): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a white solid(50 mg, 66% yield) from butyl acrylate (4c) according to GeneralProcedure B, m.p. 97.5–99.0 °C. 1H NMR (400 MHz, CDCl3): δ =0.95 (t, J = 7.4 Hz, 3 H), 1.34–1.44 (m, 2 H), 1.59–1.66 (m, 2 H),2.19 (s, 3 H), 4.13 (t, J = 6.7 Hz, 2 H), 5.65 (s, 2 H), 6.29 (d, J =15.9 Hz, 1 H), 7.28–7.33 (m, 4 H), 7.34–7.43 (m, 4 H), 7.48 (d, J= 15.9 Hz, 1 H), 7.51–7.53 (m, 1 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 13.9, 19.3, 20.9, 30.8, 54.3, 64.4, 119.9, 123.8, 124.2,127.9, 128.8, 128.9, 129.3, 130.8, 131.8, 134.8, 135.0, 138.8, 143.3,144.5, 166.9 ppm. HRMS (ESI, TOF): calcd. for C23H25N3O2 [M+ H]+ 376.2025; found 376.2029.

Cyclohexyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-methylphen-yl]acrylate (5d): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a colorless vis-cous liquid (52 mg, 65% yield) from cyclohexyl acrylate (4d) ac-cording to General Procedure B. 1H NMR (400 MHz, CDCl3): δ= 1.25–1.31 (m, 2 H), 1.37–1.46 (m, 4 H), 1.71–1.74 (m, 2 H), 1.80–1.86 (m, 2 H), 2.19 (s, 3 H), 4.78–4.84 (m, 1 H), 5.65 (s, 2 H), 6.29(d, J = 15.8 Hz, 1 H), 7.28–7.33 (m, 4 H), 7.34–7.43 (m, 4 H), 7.47(d, J = 15.9 Hz, 1 H), 7.52 (dd, J1 = 2.4, J2 = 6.6 Hz, 1 H) ppm.13C NMR (100.6 MHz, CDCl3): δ = 20.9, 23.8, 25.5, 31.8, 54.3,72.6, 120.4, 123.8, 124.1, 127.9, 128.8, 128.9, 129.3, 130.7, 131.7,134.8, 135.0, 138.8, 143.0, 144.5, 166.2 ppm. HRMS (ESI, TOF):calcd. for C25H27N3O2 [M + H]+ 402.2182; found 402.2187.

tert-Butyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-methylphen-yl]acrylate (5e): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a white solid(55 mg, 69 % yield) from tert-butyl acrylate (4e) according to Gene-ral Procedure B, m.p. 116.5–118 °C. 1H NMR (400 MHz, CDCl3):δ = 1.47 (s, 9 H), 2.18 (s, 3 H), 5.65 (s, 2 H), 6.23 (d, J = 15.9 Hz,1 H), 7.28–7.32 (m, 4 H), 7.36–7.43 (m, 5 H), 7.51 (dd, J1 = 2.3,J2 = 6.8 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 20.9,28.3, 54.3, 80.4, 121.7, 123.7, 124.1, 127.9, 128.8, 128.9, 129.4,130.8, 131.6, 134.9, 135.1, 138.8, 142.2, 144.6, 166.1 ppm. HRMS(ESI, TOF): calcd. for C23H25N3O2 [M + Na]+ 398.1844; found398.1841.

(E)-1-Benzyl-4-(2-methyl-6-styrylphenyl)-1H-1,2,3-triazole (5f): Thetitle compound was isolated by column chromatography (petro-leum/ethyl acetate = 5:1) as a white solid (42 mg, 60% yield) fromstyrene (4f) according to General Procedure B, m.p. 163.8–165.7 °C. 1H NMR (400 MHz, CDCl3): δ = 2.21 (s, 3 H), 5.64 (s,2 H), 6.82 (d, J = 16.2 Hz, 1 H), 6.92 (d, J = 16.2 Hz, 1 H), 7.19–

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7.26 (m, 5 H), 7.27–7.31 (m, 4 H), 7.33–7.35 (m, 3 H), 7.41 (s, 1H), 7.56 (d, J = 7.8 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3):δ = 21.0, 54.2, 123.2, 123.8, 126.6, 127.5, 127.6, 127.7, 128.7,128.75, 128.80, 129.2, 129.5, 130.2, 135.2, 137.5, 137.8, 138.5,145.5 ppm. HRMS (ESI, TOF): calcd. for C24H21N3 [M + H]+

352.1814; found 352.1814.

(E)-1-Benzyl-4-[2-methyl-6-(4-methylstyryl)phenyl]-1H-1,2,3-tri-azole (5g): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 5:1) as a white solid (42 mg, 58%yield) from 1-methyl-4-vinylbenzene (4g) according to General Pro-cedure B, m.p. 152.2–154.5 °C. 1H NMR (400 MHz, CDCl3): δ =2.20 (s, 3 H), 2.34 (s, 3 H), 5.64 (s, 2 H), 6.77 (d, J = 16.2 Hz, 1H), 6.89 (d, J = 16.2 Hz, 1 H), 7.07–7.19 (m, 5 H), 7.27–7.31 (m,3 H), 7.35–7.36 (m, 3 H), 7.40 (s, 1 H), 7.55 (d, J = 7.8 Hz, 1H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.0, 21.4, 54.2,123.1, 123.8, 126.5, 126.5, 127.8, 128.76, 128.79, 129.1, 129.26,129.32, 129.4, 130.1, 134.7, 135.2, 137.5, 138.0, 138.5, 145.6 ppm.HRMS (ESI, TOF): calcd. for C25H23N3 [M + H]+ 366.1970; found366.1965.

(E)-1-Benzyl-4-[2-(4-methoxystyryl)-6-methylphenyl]-1H-1,2,3-tri-azole (5h): The title compound was isolated by column chromatog-raphy (petroleum/ethyl acetate = 5:1) as a white solid (41 mg, 53%yield) from 1-methoxy-4-vinylbenzene (4h) according to GeneralProcedure B, m.p. 159.2–161.5 °C. 1H NMR (400 MHz, CDCl3): δ= 2.19 (s, 3 H), 3.81 (s, 3 H), 5.46 (s, 2 H), 6.68 (d, J = 16.2 Hz, 1H), 6.80 (d, J = 8.7 Hz, 1 H), 6.87 (d, J = 16.2 Hz, 1 H), 7.16–7.18(m, 3 H), 7.27–7.30 (m, 3 H), 7.35–7.36 (m, 3 H), 7.41 (s, 1 H),7.54 (d, J = 7.8 Hz, 1 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ= 21.0, 54.2, 55.4, 114.1, 122.9, 123.7, 125.3, 127.75, 127.80, 128.76,128.78, 129.0, 129.1, 129.3, 129.6, 130.3, 135.2, 138.1, 138.4, 145.6,159.3 ppm. HRMS (ESI, TOF): calcd. for C25H23N3O [M + H]+

382.1919; found 382.1913.

(E)-1-Benzyl-4-[2-(4-fluorostyryl)-6-methylphenyl]-1H-1,2,3-triazole(5i): The title compound was isolated by column chromatography(petroleum/ethyl acetate = 5:1) as a white solid (47 mg, 63% yield)from 1-fluoro-4-vinylbenzene (4i) according to General ProcedureB, m.p. 156.2–157.5 °C. 1H NMR (400 MHz, CDCl3): δ = 2.20 (s,3 H), 5.64 (s, 2 H), 6.72 (d, J = 16.2 Hz, 1 H), 6.87 (d, J = 16.2 Hz,1 H), 6.95 (t, J = 8.8 Hz, 2 H), 7.16–7.21 (m, 3 H), 7.27–7.32 (m,3 H), 7.34–7.37 (m, 3 H), 7.41 (s, 1 H), 7.54 (d, J = 7.8 Hz, 1H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 21.0, 54.2, 115.6 (d,J = 21.5 Hz), 123.1, 123.7, 127.22, 127.24, 127.8, 128.0 (d, J =7.9 Hz), 128.79, 128.82, 128.9, 129.2, 129.5, 133.7 (d, J = 3.1 Hz),135.2, 137.6, 138.5, 145.5, 162.3 (d, J = 247.2 Hz) ppm. HRMS(ESI, TOF): calcd. for C24H20N3F [M + H]+ 370.1720; found370.1722.

(E)-1-Benzyl-4-[2-(4-chlorostyryl)-6-methylphenyl]-1H-1,2,3-triazole(5j): The title compound was isolated by column chromatography(petroleum/ethyl acetate = 5:1) as a white solid (63 mg, 81% yield)from 1-chloro-4-vinylbenzene (4j) according to General ProcedureB, m.p. 182.3–183.5 °C. 1H NMR (400 MHz, CDCl3): δ = 2.20 (s,3 H), 5.64 (s, 2 H), 6.78 (d, J = 16.2 Hz, 1 H), 6.85 (d, J = 16.2 Hz,1 H), 7.13–7.24 (m, 5 H), 7.27–7.32 (m, 3 H), 7.34–7.37 (m, 3 H),7.41 (s, 1 H), 7.54 (d, J = 7.8 Hz, 1 H) ppm. 13C NMR (100.6 MHz,CDCl3): δ = 21.0, 54.2, 123.2, 123.7, 127.7, 127.8, 128.1, 128.79,128.81, 128.83, 129.26, 129.3, 129.7, 133.1, 135.1, 136.0, 137.4,138.5, 145.4 ppm. HRMS (ESI, TOF): calcd. for C24H20N3Cl [M+ H]+ 386.1424; found 386.1420.

Ethyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-methoxyphenyl]-acrylate (5k): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a white solid(37 mg, 51% yield) from 1-benzyl-4-(2-methoxyphenyl)-1H-1,2,3-

Ruthenium-Catalyzed Alkenylation of Arenes

triazole (1h) and ethyl acrylate (4b) according to General ProcedureB, m.p. 127.0–128.8. 1H NMR (400 MHz, CDCl3): δ = 1.29 (t, J =7.1 Hz, 3 H), 3.77 (s, 3 H), 4.21 (q, J = 7.1 Hz, 2 H), 5.63 (s, 2 H),6.36 (d, J = 15.9 Hz, 1 H), 6.96 (d, J = 8.0 Hz, 1 H), 7.29–7.35 (m,4 H), 7.36–7.43 (m, 3 H), 7.64 (s, 1 H), 7.84 (d, J = 15.9 Hz, 1H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 14.4, 54.2, 56.0, 60.5,111.9, 119.5, 120.1, 120.2, 124.9, 128.1, 128.8, 129.2, 129.5, 134.9,135.9, 141.5, 143.9, 157.4, 166.9 ppm. HRMS (ESI, TOF): calcd.for C21H21N3O3 [M + H]+ 364.1661; found 364.1660.

Ethyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-3-chlorophenyl]-acrylate (5l): The title compound was isolated by columnchromatography (petroleum/ethyl acetate = 5:1) as a white solid(48 mg, 62% yield) from 1-benzyl-4-(2-chlorophenyl)-1H-1,2,3-tri-azole (1g) and ethyl acrylate (4b) according to General ProcedureB, m.p. 138.4–140.0 °C. 1H NMR (400 MHz, CDCl3): δ = 1.28 (t,J = 7.8 Hz, 3 H), 4.20 (q, J = 7.8 Hz, 2 H), 5.67 (s, 2 H), 6.33 (d,J = 15.9 Hz, 1 H), 7.31–7.44 (m, 6 H), 7.48 (d, J = 7.9 Hz, 1 H),7.53 (d, J = 15.9 Hz, 1 H), 7.59 (d, J = 8.2 Hz, 1 H), 7.60 (s, 1H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 14.4, 54.3, 60.6,121.1, 124.6, 125.3, 128.0, 128.8, 129.3, 129.9, 130.0, 130.8, 134.7,135.2, 137.1, 142.4, 142.5, 166.4 ppm. HRMS (ESI, TOF): calcd.for C20H18N3O2Cl [M + Na]+ 390.0985; found 390.0982.

Reaction of 1-Benzyl-4-phenyl-1H-1,2,3-triazole (1a) and MethylAcrylate (4a): A mixture of 1a (0.20 mmol), 4a (0.50 mmol),Cu(OAc)2·H2O (0.44 mmol), AgSbF6 (0.04 mmol), [Ru(p-cymene)Cl2]2 (0.01 mmol), and DCE (1.5 mL) was stirred at 100 °C in asealed tube under nitrogen for 12 h. After cooling to ambient tem-perature, the products 5m and 5m� were isolated by columnchromatography on silica gel by using petroleum/ethyl acetate(from 5:1 to 10:3) as eluent.

Methyl (E)-3-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)phenyl]acrylate(5m): White solid (26 mg, 41% yield), m.p. 96.0–98.1 °C. 1H NMR(400 MHz, CDCl3): δ = 3.77 (s, 3 H), 5.63 (s, 2 H), 6.39 (d, J =15.9 Hz, 1 H), 7.33–7.47 (m, 7 H), 7.53 (s, 1 H), 7.63 (d, J = 7.7 Hz,1 H), 7.68 (d, J = 7.6 Hz, 1 H), 7.98 (d, J = 15.9 Hz, 1 H) ppm.13C NMR (100.6 MHz, CDCl3): δ = 51.9, 54.4, 120.1, 123.0, 127.3,128.2, 128.7, 128.9, 129.3, 129.8, 130.2, 130.8, 132.9, 134.7, 143.5,167.3 ppm. HRMS (EI, TOF): calcd. for C19H17N3O2 [M]+

319.1321; found 319.1320.

Dimethyl (2E,2�E)-3,3�-[2-(1-Benzyl-1H-1,2,3-triazol-4-yl)-1,3-phenylene]diacrylate (5m�): White solid (9 mg, 11% yield), m.p.153.1–155.5 °C. 1H NMR (400 MHz, CDCl3): δ = 3.74 (s, 6 H),5.68 (s, 2 H), 6.33 (d, J = 16.0 Hz, 2 H), 7.31–7.34 (m, 2 H), 7.37–7.46 (m, 5 H), 7.54 (d, J = 16.0 Hz, 2 H), 7.69 (d, J = 7.8 Hz, 2H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 51.9, 54.5, 120.5,124.9, 128.0, 128.2, 128.9, 129.4, 131.1, 134.6, 135.7, 142.7, 143.0,166.9 ppm. HRMS (EI, TOF): calcd. for C23H21N3O4 [M]+

403.1532; found 403.1540.

Supporting Information (see footnote on the first page of this arti-cle): Spectra for the products and the competition and deuteriationexperiments.

Acknowledgments

This work was supported by the National Natural Science Founda-tion of China (NSFC), by the Program for New Century ExcellentTalents in University (NCET) (NCET-13-0798), the InnovationProgram of Shanghai Municipal Education Commission (projectnumber 12ZZ050), the Basic Research Program of the ShanghaiCommittee of Science and Technology (project number

Eur. J. Org. Chem. 2014, 7878–7888 © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.eurjoc.org 7887

13NM1400802), and the Fundamental Research Funds for theCentral Universities.

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Received: July 16, 2014Published Online: October 29, 2014