DBU-Mediated Construction of 1,3,5-Trisubstituted Benzenes via

Sep 24, 2018 - A DBU-mediated synthesis of 1,3,5-trisubstituted benzenes was developed via the [2+4] annulation of in situ activated α,β-unsaturated...
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Cite This: J. Org. Chem. 2018, 83, 12507−12513

DBU-Mediated Construction of 1,3,5-Trisubstituted Benzenes via Annulation of α,β-Unsaturated Carboxylic Acids and α‑Cyano-βmethylenones Chun-Lin Zhang,† Zhao-Fei Zhang,†,‡ Zi-Hao Xia,†,‡ You-Feng Han,†,‡ and Song Ye*,†,‡ †

J. Org. Chem. 2018.83:12507-12513. Downloaded from pubs.acs.org by UNIV OF SUNDERLAND on 10/19/18. For personal use only.

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China ‡ University of Chinese Academy of Sciences, Beijing 100049, China S Supporting Information *

ABSTRACT: A DBU-mediated synthesis of 1,3,5-trisubstituted benzenes was developed via the [2 + 4] annulation of in situ activated α,β-unsaturated carboxylic acids and α-cyano-β-methylenones. The dual role of DBU as Brønsted base and nucleophilic Lewis base is the key for the success of the reaction.

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α,β-unsaturated acylammonium intermediate as 1,3-biselectropile were developed to give cyclopropanones A,3 γ-lactams B,4 dihydropyrones C,5 and benzothiazepines D.6 The bicyclic lactones E7 and F8 were also synthesized via the α,β -unsaturated acylammonium intermediate, involving the formation of three covalent bonds. In 2016, Birman and coworkers reported the isothiourea-catalyzed synthesis of thiochromenes G by further decarboxylation of the generated bicyclic β-lactones.9 In this work, we report the synthesis of 1,3,5-trisubstituted benzenes H via the DBU-catalyzed generation of α,β-unsaturated acylammonium intermediate. Benzene is a fundamental unit commonly found in numerous natural products10 and bioactive molecules.11 Among them, 1,3,5-trisubstituted benzenes are valuable building blocks and widely employed in materials such as amorphous molecular materials,12 organic frameworks,13 fluorescent sensor,14 and ligands.15 Recently, the contrusction of benzene via N-heterocyclic carbene catalysis has been reported by the groups of Chi,16 Lupton,17 and Fang.18 Wang and we independently developed an oxidative NHC-catalyzed synthesis of benzonitrile derivatives by [2 + 4] annulation of enals with α-cyano-β-methylenones.19 Soon after that, we reported the synthesis of 1,3,5-trisubstituted benzenes from αbromoenals by decyanolative aromatization.20 α-Bromoenal was used to generate α,β-unsaturated acyl azolium under NHC catalysis to avoid the use of oxidant. The requirement of the preparation of α-bromoenals and NHC catalysts in the work prompted us to develop an alternative convenient method for the synthesis of 1,3,5-trisubstituted benzenes. We envisioned that the α,β-unsaturated acylammonium intermediate could react with α-cyano-β-methylenones to give bicyclic β-lactones,

INTRODUCTION Being readily available and easy to handle, carboxylic acids are one of the most commonly employed starting materials for chemical transformations. Recently, the Lewis base-catalyzed annulation of carboxylic acids has been developed for the construction of structurally diverse molecules.1 However, α,βunsaturated acylammonium intermediate generated from α,βunsaturated carboxylic acids and their derivatives under tertiary amine catalysis has received much less attention (Scheme 1).2 Possessing two electrophilic sites at C1 and C3 positions and a latent nucleophilic site at C2 position, this intermediate is particularly useful for the synthesis of cyclic compounds. For example, a series of [3 + 2], [3 + 3], and [3 + 4] annulations of Scheme 1. Synthesis of Cyclic Compounds via Catalytic Generation of α,β-Unsaturated Acylammonium Intermediate

Received: July 10, 2018 Published: September 24, 2018 © 2018 American Chemical Society

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DOI: 10.1021/acs.joc.8b01740 J. Org. Chem. 2018, 83, 12507−12513

Article

The Journal of Organic Chemistry

Table 2. Scope of α,β-Unsaturated Carboxylic Acida

followed by decarboxylation and aromatization to afford 1,3,5trisubstituted benzenes.

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RESULTS AND DISCUSSION The model reaction of cinnamic acid 1a and α-cyano-βmethylenone 2a was carried out with nucleophilic catalyst (Table 1). We were encouraged to find that the reaction with Table 1. Reaction Optimizationa

entry

additives

base

solvent

yield (%)b

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

CDI HATU EDC·HCl/DMAP DCC/DMAP CDI CDI CDI CDI CDI CDI CDI CDI CDI CDI CDIf

DBU DBU DBU DBU DBU DBU DBU DBU DBU DMAP DABCO DIPEA Cs2CO3 DBU DBU

toluene toluene toluene toluene THF Et2O CH3CN DCM 1,4-dioxane THF THF THF THF THF THF

57 18 26 15 67 52 52 64 43 0 0 0 10 72 34

a

Reaction conditions: 1 (0.4 mmol) and CDI (0.4 mmol) were stirred for 2 h, and then 2a (0.2 mmol) and DBU (0.5 mmol) were added to the reaction mixture.

a

Reaction conditions: 1a (0.4 mmol), 2a (0.2 mmol), additive (0.4 mmol), and base (0.5 mmol) at room temperature. bYield of the isolated product. c2.0 equiv of EDC·HCl and 0.2 equiv of DMAP were used. d2.0 equiv of DCC and 0.2 equiv of DMAP were used. e1a and CDI were stirred for 2 h, and then 2a and DBU were added to the reaction mixture. f1.2 equiv of CDI was used.

and 2-BrC6H4) were also tolerated for the reaction to afford the corresponding products 3g−3j in good yields. All the reactions of β-disubstituted aryl (R = 2,5-Cl2C6H3, 3,4Cl2C6H3) or β-heteroaryl (R = 3-pyridinyl, 2-furyl) α,βunsaturated carboxylic acids worked smoothly (3k−3n). In addition, fumaric acid monoester was also feasible for the reaction to give benzoate 3o in 58% yield. However, α,βunsaturated carboxylic acids with β-aliphatic substituents (R = Me, n-Pr) did not work under the standard condition. The scope of enones was then explored (Table 3). Both βarylenones with electron-donating (R′ = 4-MeOC6H4, 4MeC6H4) and those with electron-withdrawing substituents (R′ = 4-ClC6H4, 4-BrC6H4, 4-NO2C6H4) worked well to give 1,3,5-triarylbenzenes (3p−3t) in moderate to good yields. βArylenones with meta- (R′ = 3-MeC6H4, 3-ClC6H4) or orthosubstituents (R′ = 2-MeC6H4, 2-ClC6H4) were also tolerated to afford the corresponding products in good yields (3u−3x). The reaction of the enone with bulky β-naphthyl went smoothly to give the triarylbenzene 3y in 68% yield. The reaction of β-heteroarylenone (R′ = 2-thienyl) afforded the product 3z in 61% yield. It should be pointed out that β,βdialkylenones, which did not work in our previous work, provided the corresponding products with acceptable yields (3za−3zb). Furthermore, aryl enone with electron-donating (R″ = 4-MeOC6H4), electron-withdrawing (R″ = 4-FC6H4), or heteroaryl groups (R″ = 2-thienyl) all worked well to afford the products in good yields (3zc−3ze). It is worth noting that the reaction of alkyl enone (R″ = methyl) gave 1,3,5-alkyldiarylbenzene 3zf with decreased but still acceptable yield (39%). However, other enones with α-CO2Et and α-Bz failed to give

N,N′-carbonyldiimidazole (CDI) as the additive to activate carboxylic acid and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as Brønsted base and nucleophilic catalyst gave the desired 1,3,5-triphenylbenzene 3a in 57% yield (entry 1). Other acidactivating reagents, such as 1-[bis(dimethylamino)methylene]1H- 1,2,3-triazolo[4,5-b]pyridinium 3-oxid-hexafluorophosphate (HATU), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC·HCl), or dicyclohexylcarbodiimide (DCC), resulted in lower yields (entries 2−4). Screening of solvents revealed that THF performed best to afford the product in 67% yield (entry 5 vs 6−9). The reaction using DMAP, DABCO, or DIPEA instead of DBU gave no desired product (entries 10−12), while very low yield was resulted when Cs2CO3 was used (entry 13). The yield was improved to 72% when the reaction was carried out by premixing of the cinnamic acid 1a and CDI for 2 h before the addition of DBU and enone 2a (entry 14). Reducing the loading of the additive to 1.2 equivalence led to dramatical loss of the yield (entry 15). With the optimized conditions in hand, the scope of α,βunsaturated carboxylic acids was then investigated (Table 2). Both electron-donating (R = 4-MeOC6H4, 4-MeC6H4) and electron-withdrawing groups (R = 4-ClC6H4, 4-BrC6H4, 4NO2C6H4) worked well to give the desired 1,3,5-triarylbenzenes 3b−3f in good yields. meta-Substituents (R = 3MeC6H4, 3-BrC6H4) and ortho-substituents (R = 2-MeC6H4 12508

DOI: 10.1021/acs.joc.8b01740 J. Org. Chem. 2018, 83, 12507−12513

Article

The Journal of Organic Chemistry Table 3. Scope of Enonesa

a

Reaction conditions: 1 (0.4 mmol) and CDI (0.4 mmol) were stirred for 2 h, and then 2 (0.2 mmol) and DBU (0.5 mmol) were added to the reaction mixture.

the α,β-unsaturated acylammonium intermediate I,21 The reaction of enone 2 with intermediate 1 via the Diels−Alder reaction of its dienolate 2′ affords the adduct II. The lactonization of adduct II gives bicyclic β-lactone III and releases the catalyst of DBU. The decarboxylation of adduct III delivers cyclohexadiene IV, which undergoes decyanolative aromatization to afford 1,3,5-trisubstituted benzene 3 in the presence of base.20 To clarify the mechanistic hypothesis, several control experiments were conducted (Scheme 2). It was found that the reaction of α,β-unsaturated N-acyl imidazole 1a′ and enone 2a in the presence of 20 mol % of DBU gave the product 3a in good yield, while very low yield was resulted in the absence of DBU (Scheme 2, reaction 1). These results suggest the unique role of DBU as the nucleophilic catalyst for the reaction. Deuterium experiment revealed 56% deuteriumlabeled 1,3,5-trisubstitued benzene 3q was isolated in 71% yield when cyanocyclohexadiene IV-q′20 was subjected to the decyanolative aromatization condition in the presence of D2O as the additive (Scheme 2, reaction 2). The deuterium incorporation supports the mechanism involving deprotonation/protanation for the decyanolative aromatization of the cyanocyclohexadienes.

benzene or cyclohexadiene derivatives under the standard conditions. A proposed catalytic cycle is illustrated in Figure 1. The addition of DBU to α,β-unsaturated N-acyl imidazole 1′, formed in situ from the α,β-unsaturated carboxylic acid, gives

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CONCLUSION In conclusion, the synthesis of 1,3,5-trisubstituted benzenes by DBU-mediated annulation of α,β-unsaturated carboxylic acids

Figure 1. Proposed catalytic cycle. 12509

DOI: 10.1021/acs.joc.8b01740 J. Org. Chem. 2018, 83, 12507−12513

Article

The Journal of Organic Chemistry

1609, 1594, 1514, 1497, 1251, 1179, 832, 757, 698. HRMS (APCIorbitrap) m/z: Calc. for C25H21O ([M + H]+) 337.1587, Found 337.1582. 4-Methyl-5′-phenyl-1,1′:3′,1″-terphenyl (3c)24 (ZCL-833) Yield. 35 mg, 55%, white solid, mp 116−117 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83−7.82 (m, 3H), 7.76 (d, J = 1.5 Hz, 4H), 7.52 (t, J = 7.3 Hz, 2H), 7.45−7.43 (q, J = 8.6 Hz, 4H), 7.42 (t, J = 7.5 Hz, 2H), 7.34 (t, J = 7.3 Hz, 2H), 2.47 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.44, 142.38, 141.4, 138.4, 137.5, 129.7, 129.0, 127.6, 127.5, 127.3, 125.12, 125.07, 21.3. IR (KBr) ν 1596, 1515, 1497, 1264, 877, 815, 764, 702. HRMS (APCI-orbitrap) m/z: Calc. for C25H20 (M +) 320.1560, Found 320.1554. 4-Chloro-5′-phenyl-1,1′:3′,1″-terphenyl (3d)24 (ZCL-823) Yield. 52 mg, 76%, white solid, mp 137−138 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83 (t, J = 1.5 Hz, 1H), 7.77 (d, J = 1.6 Hz, 2H), 7.75−7.70 (m, 4H), 7.65 (d, J = 8.5 Hz, 2H), 7.54−7.42 (m, 8H). 13C NMR (100 MHz, CDCl3) δ 142.6, 141.2, 141.1, 139.7, 133.8, 129.1, 129.0, 128.7, 127.8, 127.5, 125.6, 125.1. IR (KBr) ν 1596, 1494, 1092, 832, 760, 701. HRMS (APCI-orbitrap) m/z: Calc. for C24H17Cl (M+) 340.1013, Found 340.1011. 4-Bromo-5′-phenyl-1,1′:3′,1″-terphenyl (3e)24 (ZCL-822) Yield. 57 mg, 74%, white solid, mp 144−145 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83 (s, 1H), 7.76 (d, J = 1.5 Hz, 2H), 7.72 (d, J = 7.3 Hz, 4H), 7.61 (q, J = 8.6 Hz, 4H), 7.52 (t, J = 7.5 Hz, 4H), 7.43 (t, J = 7.3 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 142.7, 141.2, 141.0, 140.1, 132.1, 129.04, 129.02, 127.8, 127.5, 125.7, 125.0, 122.0. IR (KBr) ν 1595, 1489, 1383, 1074, 829, 819, 758, 699. HRMS (APCI-orbitrap) m/z: Calc. for C24H17Br (M+) 384.0508, Found 384.0503. 1-(5′-Phenyl-[1,1′:3′,1″-terphenyl]-4-yl)ethan-1-one (3f)25 (ZCL888) Yield. 50 mg, 72%, white solid, mp 102−103 °C, Rf = 0.40 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 6.8 Hz, 2H), 7.85−7.79 (m, 5H), 7.72−7.70 (m, 4H), 7.52−7.51 (m, 4H), 7.46−7.38 (m, 2H), 2.67 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 197.8, 145.8, 142.8, 141.1, 141.0, 136.2, 129.1, 129.0, 127.9, 127.6, 127.5, 126.2, 125.3, 26.8. IR (KBr) ν 2921, 1723, 1680, 1595, 1269, 760, 699. HRMS (APCI-orbitrap) m/z: Calc. for C26H21O ([M + H]+) 349.1587, Found 349.1580. 3-Methyl-5′-phenyl-1,1′:3′,1″-terphenyl (3g) (ZCL-827) Yield. 43 mg, 67%, white solid, mp 145−146 °C, Rf = 0.37 (petroleum ether/ ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.68 (s, 3H), 7.60 (d, J = 7.5 Hz, 4H), 7.42−7.36 (m, 6H), 7.30−7.27 (m, 3H), 7.12−7.10 (m, 1H), 2.35 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.6, 142.4, 141.32, 141.26, 138.6, 129.0, 128.9, 128.4, 128.3, 127.7, 127.5, 125.3, 125.2, 124.6, 21.7. IR (KBr) ν 1593, 1496, 1413, 1180, 878, 788, 764, 699. HRMS (APCI-orbitrap) m/z: Calc. for C25H20 (M+) 320.1560, Found 320.1557. 3-Bromo-5′-phenyl-1,1′:3′,1″-terphenyl (3h) (ZCL-829) Yield. 55 mg, 71%, white solid, mp 100−101 °C, Rf = 0.45 (petroleum ether/ ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.88−7.84 (m, 2H), 7.77−7.71 (m, 6H), 7.65 (d, J = 7.7 Hz, 1H), 7.56−7.50 (m, 5H), 7.44 (t, J = 7.3 Hz, 2H), 7.37 (t, J = 7.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 143.4, 142.6, 141.0, 140.9, 130.6, 130.49, 130.48, 129.0, 127.8, 127.5, 126.1, 125.9, 125.2, 123.1. IR (KBr) ν 1591, 1561, 1497, 1411, 1391, 1073, 873, 757, 696. HRMS (APCI-orbitrap) m/z: Calc. For C24H17Br (M+) 384.0508, Found 384.0502. 2-Methyl-5′-phenyl-1,1’:3′,1’’-terphenyl (3i)20 (ZCL-828) Yield. 40 mg, 63%, white solid, mp 103−104 °C, Rf = 0.43 (petroleum ether/ ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83 (t, J = 1.7 Hz, 1H), 7.73−7.71 (m, 4H), 7.59 (d, J = 1.7 Hz, 2H), 7.52−7.48 (m, 4H), 7.42−7.38 (m, 3H), 7.36−7.31 (m, 3H), 2.41 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 143.1, 141.9, 141.7, 141.2, 135.6, 130.6, 130.0, 129.0, 127.6, 127.4, 127.2, 126.0, 124.7, 20.8. IR (KBr) ν 1593, 1495, 1411, 882, 754, 696. HRMS (APCI-orbitrap) m/z: Calc. for C25H20 (M+) 320.1560, Found 320.1556. 2-Bromo-5′-phenyl-1,1′:3′,1″-terphenyl (3j)20 (ZCL-830) Yield. 50 mg, 65%, white solid, mp 98−99 °C, Rf = 0.42 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.74 (s, 1H), 7.62−

Scheme 2. Control Experiments

and α-cyano-β-methylenones was developed. The reaction features readily available starting materials and metal-free and mild conditions. Other related construction of multisubstituted benzenes is underway in our laboratory.

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EXPERIMENTAL SECTION

General Information. Unless otherwise indicated, all reactions were carried out under an N2 atmosphere in oven-dried glassware with magnetic stirring. Anhydrous THF, Et2O, 1,4-dioxane, and toluene were distilled from sodium and benzophenone, CH3CN and CH2Cl2 were distilled from CaH2. Enones were synthesized according to literature.22 α,β-Unsaturated carboxylic acids were used as received from comercially available sources. Typical Procedure for the DBU-Mediated Construction of 1,3,5Trisubstituted Benzenes. An oven-dried 25 mL Schlenk tube equipped with a stir bar was charged with α,β-unsaturated carboxylic acid 1a (59.2 mg, 0.4 mmol) and N,N′- carbonyldiimidazole (CDI) (64.8 mg, 0.4 mmol). This tube was closed with a septum, evacuated, and backfilled with nitrogen. To this mixture was added freshly distilled THF (1 mL). The reaction mixture was stirred at room temperature for 2 h, and then DBU (76 mg, 0.5 mmol) and enone 2a (49.4 mg, 0.2 mmol, dissolved in 1 mL of THF) were added via a syringe. The reaction mixture was stirred at room tempreture until complete consumption of the starting material as monitored by TLC (typically 12 h). The reaction mixture was diluted by THF, filtered through a short silica columm, and then concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (petroleum ether/Et 2 O = 100:1) to furnish the corresponding product 3a (44 mg, 72% yield). 5′-Phenyl-1,1′:3′,1″-terphenyl (3a)23 (ZCL-766) Yield. 44 mg, 72%, white solid, mp 167−168 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83c (s, 3H), 7.75 (d, J = 7.2 Hz, 6H), 7.52 (t, J = 7.6 Hz, 6H), 7.43 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 142.5, 141.3, 129.0, 127.7, 127.5, 125.3. IR (KBr) ν 1594, 1497, 750, 700. HRMS (APCI-orbitrap) m/z: Calc. for C24H18 (M+) 306.1403, Found 306.1402. 4-Methoxy-5′-phenyl-1,1′:3′,1″-terphenyl (3b)24 (ZCL-834) Yield. 35 mg, 52%, white solid, mp 133−134 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.78 (s, 3H), 7.73 (d, J = 7.5 Hz, 4H), 7.66 (d, J = 8.7 Hz, 2H), 7.51 (t, J = 7.6 Hz, 4H), 7.42 (t, J = 7.3 Hz, 2H), 7.04 (d, J = 8.7 Hz, 2H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.5, 142.4, 142.0, 141.4, 133.8, 129.0, 128.5, 127.6, 127.5, 124.9, 124.8, 114.4, 55.5. IR (KBr) ν 12510

DOI: 10.1021/acs.joc.8b01740 J. Org. Chem. 2018, 83, 12507−12513

Article

The Journal of Organic Chemistry

HRMS (APCI-orbitrap) m/z: Calc. for C25H19Br (M+) 398.0665, Found 398.0660. 4-Bromo-4’’-chloro-5′-phenyl-1,1′:3′,1″-terphenyl (3r)20 (ZCL844) Yield. 45 mg, 54%, white solid, mp 164−165 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.75−7.74 (m, 2H), 7.70−7.68 (m, 3H), 7.62 (d, J = 8.6 Hz, 4H), 7.56−7.52 (m, 2H), 7.51−7.48 (m, 2H), 7.47−7.45 (m, 2H), 7.44− 7.40 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 142.9, 141.4, 140.9, 140.0, 139.5, 133.9, 132.1, 129.2, 129.1, 129.0, 128.7, 127.9, 127.5, 125.4, 125.3, 124.8, 122.1. IR (KBr) ν 1597, 1489, 1381, 1091, 1010, 878, 808, 754, 692. HRMS (APCI-orbitrap) m/z: Calc. for C24H16BrCl (M+) 418.0118, Found 418.0114. 4,4″-Dibromo-5′-phenyl-1,1′:3′,1″-terphenyl (3s)20 (ZCL-843) Yield. 59 mg, 64%, white solid, mp 170−171 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 1.5 Hz, 2H), 7.69−7.67 (m, 3H), 7.61 (d, J = 8.5 Hz, 4H), 7.55 (d, J = 8.6 Hz, 4H), 7.50 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.3 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 142.9, 141.4, 140.9, 139.9, 132.1, 129.1, 129.0, 127.9, 127.5, 125.4, 124.7, 122.1. IR (KBr) ν 1595, 1487, 1379, 1070, 1007, 807, 753, 692. HRMS (APCI-orbitrap) m/z: Calc. for C24H16Br2 (M+) 461.9613, Found 461.9610. 4-Bromo-4″-nitro-5′-phenyl-1,1′:3′,1″-terphenyl (3t)20 (ZCL-847) Yield. 63 mg, 73%, white solid, mp 192−193 °C, Rf = 0.35 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 8.34 (d, J = 8.8 Hz, 2H), 7.85−7.80 (m, 4H), 7.75−7.74 (m, 1H), 7.70−7.67 (m, 2H), 7.62 (d, J = 8.5 Hz, 2H), 7.56 (d, J = 8.5 Hz, 2H), 7.51 (t, J = 7.5 Hz, 2H), 7.43 (t, J = 7.3 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 147.5, 143.2, 141.8, 140.5, 140.3, 139.6, 132.2, 129.2, 129.0, 128.19, 128.16, 127.4, 126.6, 125.7, 125.1, 124.3, 122.4. IR (KBr) ν 1592, 1514, 1488, 1345, 1006, 849, 811, 750, 689. HRMS (EI-TOF) m/z: Calc. for C24H16NO2Br (M+) 429.0364, Found 429.0364. 4″-Bromo-3-methyl-5′-phenyl-1,1′:3′,1″-terphenyl (3u)20 (ZCL891) Yield. 58 mg, 73%, white solid, mp 114−115 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.69 (t, J = 1.6 Hz, 1H), 7.63 (d, J = 1.6 Hz, 2H), 7.60−7.58 (m, 2H), 7.52−7.45 (m, 4H), 7.40−7.37 (m, 4H), 7.32−7.28 (m, 2H), 7.14− 7.11 (m, 1H), 2.36 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.8, 142.6, 141.2, 141.1, 141.0, 140.2, 138.7, 132.1, 129.1, 129.0, 128.9, 128.5, 128.2, 127.8, 127.5, 125.7, 125.0, 124.9, 124.6, 121.9, 21.7. IR (KBr) ν 1595, 1489, 1383, 1074, 1008, 877, 822, 785, 760, 700. HRMS (APCI-orbitrap) m/z: Calc. for C25H19Br (M+) 398.0665, Found 398.0660. 4″-Bromo-3-chloro-5′-phenyl-1,1′:3′,1″-terphenyl (3v)20 (ZCL893) Yield. 56 mg, 67%, wax, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 1.6 Hz, 2H), 7.69 (d, J = 7.5 Hz, 4H), 7.63−7.61 (m, 2H), 7.57−7.55 (m, 3H), 7.52−7.49 (m, 2H), 7.44−7.37 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 142.88, 142.86, 141.4, 141.2, 140.8, 139.9, 134.9, 132.1, 130.3, 129.1, 129.0, 127.9, 127.8, 127.6, 127.5, 125.62, 125.57, 125.55, 124.9, 122.1. IR (KBr) ν 1592, 1489, 1383, 1074, 1008, 875, 821, 762, 696. HRMS (APCI-orbitrap) m/z: Calc. for C24H16ClBr (M+) 418.0118, Found 418.0112. 4″-Bromo-2-methyl-5′-phenyl-1,1′:3′,1″-terphenyl (3w)20 (ZCL892) Yield. 44 mg, 55%, white solid, mp 132−133 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.76 (t, J = 1.7 Hz, 1H), 7.70−7.68 (m, 2H), 7.62−7.55 (m, 5H), 7.52−7.47 (m, 3H), 7.42−7.38 (m, 1H), 7.36−7.29 (m, 4H), 2.38 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 143.3, 141.9, 141.6, 141.0, 140.5, 140.1, 135.5, 132.1, 130.6, 129.9, 129.0, 127.7, 127.5, 127.4, 126.9, 126.0, 124.5, 121.9, 20.7. IR (KBr) ν 1593, 1489, 1072, 1007, 821, 757, 698. HRMS (APCI-orbitrap) m/z: Calc. for C25H19Br (M+) 398.0665, Found 398.0661. 4″-Bromo-2-chloro-5′-phenyl-1,1′:3′,1″-terphenyl (3x)20 (ZCL894) Yield. 46 mg, 55%, white solid, mp 112−113 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.78 (t, J = 1.5 Hz, 1H), 7.70−7.68 (m, 3H), 7.63−7.52 (m, 6H), 7.50−7.44 (m, 3H), 7.41−7.33 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 142.0, 140.9, 140.6, 140.5, 140.2, 140.0, 132.7, 132.1, 131.5, 130.2, 129.1, 129.0, 127.82, 127.80, 127.5, 127.2, 127.1, 125.2, 122.0.

7.59 (m, 5H), 7.54 (d, J = 1.5 Hz, 2H), 7.38−7.33 (m, 5H), 7.30− 7.27 (m, 3H), 7.15−7.10 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 142.5, 142.1, 141.6, 141.0, 133.4, 131.5, 129.1, 129.0, 127.7, 127.6, 127.5, 127.4, 125.4, 122.8. IR (KBr) ν 1594, 1497, 1475, 1410, 1263, 1024, 882, 754, 697. HRMS (APCI-orbitrap) m/z: Calc. for C24H17Br (M+) 384.0508, Found 384.0503. 2,6-Dichloro-5′-phenyl-1,1′:3′,1″-terphenyl (3k) (ZCL-838) Yield. 59 mg, 79%, white solid, mp 154−155 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.77 (s, 1H), 7.59 (d, J = 7.4 Hz, 4H), 7.40 (d, J = 1.5 Hz, 2H), 7.37−7.32 (m, 6H), 7.26 (t, J = 7.3 Hz, 2H), 7.15−7.11 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 141.8, 140.9, 139.5, 137.9, 135.2, 129.3, 128.9, 128.3, 127.7, 127.5, 127.4, 125.8. IR (KBr) ν 1595, 1556, 1428, 1191, 782, 760, 698. HRMS (APCI-orbitrap) m/z: Calc. for C24H16Cl2 (M+) 374.0624, Found 374.0618. 3,4-Dichloro-5′-phenyl-1,1′:3′,1″-terphenyl (3l) (ZCL-883) Yield. 55 mg, 73%, wax, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83 (t, J = 1.5 Hz, 1H), 7.79 (d, J = 1.5 Hz, 1H), 7.72−7.69 (m, 6H), 7.57−7.49 (m, 6H), 7.42 (t, J = 7.3 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 142.8, 141.3, 140.9, 140.0, 133.1, 131.9, 130.9, 129.3, 129.1, 127.9, 127.5, 126.7, 126.1, 125.0. IR (KBr) ν 1595, 1496, 1478, 1134, 1029, 872, 758, 698. HRMS (APCIorbitrap) m/z: Calc. for C24H16Cl2 (M+) 374.0624, Found 374.0620. 3-([1,1′:3′,1″-Terphenyl]-5′-yl)pyridine (3m) (ZCL-825) Yield. 55 mg, 90%, white solid, mp 148−149 °C, Rf = 0.10 (petroleum ether/ ethyl acetate, 5:1). 1H NMR (400 MHz, CDCl3) δ 8.99 (s, 1H), 8.66 (d, J = 3.8 Hz, 1H), 7.99 (d, J = 7.6 Hz, 1H), 7.86 (s, 1H), 7.78 (s, 2H), 7.71 (d, J = 7.3 Hz, 4H), 7.51 (t, J = 7.3 Hz, 4H), 7.44−7.41 (m, 3H). 13C NMR (100 MHz, CDCl3) δ 148.9, 148.6, 142.8, 140.8, 139.1, 136.7, 134.6, 129.0, 127.9, 127.4, 126.0, 125.1, 123.7. IR (KBr) ν 1595, 1498, 1180, 1076, 879, 757, 698. HRMS (APCI-orbitrap) m/ z: Calc. for C23H18N ([M + H]+) 308.1434, Found 308.1429. 2-([1,1′:3′,1″-Terphenyl]-5′-yl)furan (3n) (ZCL-826) Yield. 35 mg, 59%, white solid, mp 102−103 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 1.6 Hz, 2H), 7.73−7.71 (m, 5H), 7.54−7.49 (m, 5H), 7.44−7.40 (m, 2H), 6.80 (d, J = 3.3 Hz, 1H), 6.54 (dd, J = 3.3, 1.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 154.0, 142.4, 141.1, 131.9, 129.0, 127.7, 127.4, 125.4, 121.7, 111.9, 105.7. IR (KBr) ν 1595, 1494, 1430, 1218, 1010, 876, 757, 698. HRMS (APCI-orbitrap) m/z: Calc. for C22H17O ([M + H]+) 297.1274, Found 297.1268. Ethyl [1,1′:3′,1″-terphenyl]-5′-Carboxylate (3o)26 (ZCL-839) Yield. 35 mg, 58%, white solid, mp 111−112 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 8.27 (d, J = 1.6 Hz, 2H), 8.00 (s, 1H), 7.69 (d, J = 7.3 Hz, 4H), 7.49 (t, J = 7.5 Hz, 4H), 7.41 (t, J = 7.3 Hz, 2H), 4.45 (q, J = 7.1 Hz, 2H), 1.45 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 166.7, 142.2, 140.4, 131.7, 130.4, 129.1, 128.0, 127.4, 127.2, 61.3, 14.5. IR (KBr) ν 1716, 1338, 1238, 1058, 754, 698. HRMS (APCI-orbitrap) m/z: Calc. for C21H19O2 ([M + H]+) 303.1380, Found 303.1374. 4-Bromo-4″-methoxy-5′-phenyl-1,1′:3′,1″-terphenyl (3p)20 (ZCL841) Yield. 42 mg, 51%, white solid, mp 112−113 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.77−7.76 (m, 1H), 7.70−7.68 (m, 4H), 7.65−7.55 (m, 6H), 7.50 (t, J = 7.5 Hz, 2H), 7.41 (t, J = 7.3 Hz, 1H), 7.03 (d, J = 8.7 Hz, 2H), 3.88 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.6, 142.7, 142.3, 141.2, 140.3, 133.6, 132.1, 129.1, 129.0, 128.5, 127.8, 127.5, 125.3, 124.6, 124.5, 121.9, 114.5, 55.5. IR (KBr) ν 1609, 1595, 1514, 1489, 1288, 1250, 1179, 1008, 802, 761, 699. HRMS (APCI-orbitrap) m/z: Calc. for C25H19OBr (M +) 414.0614, Found 414.0607. 4-Bromo-4″-methyl-5′-phenyl-1,1′:3′,1″-terphenyl (3q)20 (ZCL842) Yield. 53 mg, 66%, white solid, mp 133−134 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.82 (s, 1H), 7.75−7.74 (m, 2H), 7.72−7.70 (d, J = 7.6 Hz, 2H) 7.64−7.57 (m, 6H), 7.51 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.3 Hz, 1H), 7.32 (d, J = 7.9 Hz, 2H), 2.45 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.63, 142.57, 141.17, 141.15, 140.2, 138.2, 137.6, 132.1, 129.7, 129.1, 129.0, 127.7, 127.5, 127.3, 125.5, 124.82, 124.76, 121.9, 21.3. IR (KBr) ν 1595, 1514, 1489, 1381, 1074, 1007, 881, 811, 761, 700. 12511

DOI: 10.1021/acs.joc.8b01740 J. Org. Chem. 2018, 83, 12507−12513

Article

The Journal of Organic Chemistry IR (KBr) ν 1490, 1073, 1007, 815, 755, 698. HRMS (APCI-orbitrap) m/z: Calc. for C24H16ClBr (M+) 418.0118, Found 418.0112. 2-(4-Bromo-[1,1′:3′,1″-terphenyl]-5′-yl)naphthalene (3y)20 (ZCL845) Yield. 59 mg, 68%, wax, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 8.16 (s, 1H), 7.99− 7.90 (m, 4H), 7.88−7.84 (m, 2H), 7.79 (d, J = 1.4 Hz, 1H), 7.74 (d, J = 7.3 Hz, 2H), 7.65−7.59 (m, 4H), 7.58−7.51 (m, 4H), 7.44 (t, J = 7.3 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 142.8, 142.6, 141.3, 141.1, 140.2, 138.3, 133.8, 132.9, 132.1, 129.1, 129.0, 128.7, 128.4, 127.8, 127.5, 126.6, 126.3, 126.2, 125.9, 125.7, 125.2, 125.1, 122.0. IR (KBr) ν 1593, 1489, 1072, 1008, 816, 759, 699. HRMS (APCIorbitrap) m/z: Calc. for C28H19Br (M+) 434.0665, Found 434.0660. 2-(4-Bromo-[1,1′:3′,1″-terphenyl]-5′-yl)thiophene (3z)20 (ZCL846) Yield. 48 mg, 61%, white solid, mp 107−108 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.83 (t, J = 1.5 Hz, 1H), 7.76 (t, J = 1.6 Hz, 1H), 7.70−7.67 (m, 3H), 7.63−7.60 (m, 2H), 7.56−7.54 (m, 2H), 7.51 (t, J = 7.5 Hz, 2H), 7.44−7.42 (m, 2H), 7.35−7.34 (m, 1H), 7.14 (dd, J = 5.0, 3.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 144.1, 142.8, 141.4, 140.8, 139.9, 135.7, 132.1, 129.02, 128.2, 127.9, 127.4, 125.4, 125.2, 124.3, 123.8, 123.7, 122.1. IR (KBr) ν 1595, 1488, 1415, 1383, 1075, 1007, 825, 760, 698. HRMS (APCI-orbitrap) m/z: Calc. for C22H15SBr (M+) 390.0072, Found 390.0069. 5′-Propyl-1,1′:3′,1″-terphenyl (3za) (ZCL-1541) Yield. 21 mg, 39%, wax, Rf = 0.5 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.66−7.63 (m, 5H), 7.48−7.44 (t, J = 7.5 Hz, 4H), 7.40 (s, 2H), 7.38−7.35 (t, J = 7.5 Hz, 2H), 2.73 (t, J = 7.5 Hz, 2H), 1.75 (m, 2H), 1.01 (t, J = 7.5 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 143.8, 141.9, 141.6, 128.9, 127.4, 126.6, 123.8, 38.4, 24.8, 14.1. IR (KBr) ν 1596, 1498, 1433, 1260, 1075, 1029, 882, 757, 697. HRMS (APCI-orbitrap) m/z: Calc. for C21H20 (M+) 272.1560, Found 272.1559. 5′-Isobutyl-1,1′:3′,1″-terphenyl (3zb) (ZCL-1535) Yield. 25 mg, 44%, wax, Rf = 0.5 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.67−7.66 (m, 2H), 7.65−7.64 (m, 3H), 7.48− 7.45 (m, 4H), 7.39−7.35 (m, 4H), 2.62 (d, J = 7.0 Hz, 2H), 1.98 (m, 1H), 0.98 (d, J = 6.5 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 142.8, 141.7, 141.6, 128.9, 127.44, 127.41, 127.2, 123.8, 45.8, 30.5, 22.6. IR (KBr) ν 1596, 1498, 1455, 1433, 1383, 1029, 877, 756, 696. HRMS (APCI-orbitrap) m/z: Calc. for C22H22 (M+) 286.1716, Found 286.1715. 4-Bromo-4″-methoxy-5′-phenyl-1,1′:3′,1″-terphenyl (3zc/3p)20 (ZCL-848) Yield. 54 mg, 65%, white solid, mp 111−112 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.78 (s, 1H), 7.71−7.69 (m, 4H), 7.65−7.56 (m, 6H), 7.52−7.48 (m, 2H), 7.44−7.40 (m, 1H), 7.04 (d, J = 8.7 Hz, 2H), 3.89 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 159.6, 142.6, 142.2, 141.2, 140.3, 133.5, 132.1, 129.03, 129.0, 128.5, 127.7, 127.5, 125.2, 124.6, 124.5, 121.9, 114.5, 55.5. IR (KBr) ν 1609, 1595, 1514, 1489, 1288, 1250, 1179, 1073, 1008, 820, 761, 699. HRMS (APCI-orbitrap) m/z: Calc. for C25H19OBr (M+) 414.0614, Found 414.0606. 4-Bromo-4″-fluoro-5′-phenyl-1,1′:3′,1″-terphenyl (3zd)20 (ZCL849) Yield. 58 mg, 72%, white solid, mp 131−132 °C, Rf = 0.45 (petroleum ether/ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.75−7.74 (m, 2H), 7.70−7.60 (m, 7H), 7.56 (d, J = 8.5 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.3 Hz, 1H), 7.18 (t, J = 8.7 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 161.3 (d, J = 247.5 Hz), 142.8, 141.7, 141.3, 141.0, 140.1, 137.2 (d, J = 4.04 Hz), 132.1, 129.08, 129.04, 129.00, 127.9, 127.5, 125.5, 125.0, 124.9, 122.1, 115.9 (d, 20.2 Hz). IR (KBr) ν 1601, 1509, 1489, 1224, 1074, 1007, 817, 754, 692. HRMS (APCI-orbitrap) m/z: Calc. for C24H16BrF (M+) 402.0414, Found 402.0410. 3-(5-(Thiophen-2-yl)-[1,1′-biphenyl]-3-yl)pyridine (3ze) (ZCL884) Yield. 52 mg, 83%, white solid, mp 113−114 °C, Rf = 0.15 (petroleum ether/ethyl acetate, 5:1). 1H NMR (500 MHz, CDCl3) δ 8.95 (d, J = 1.9 Hz, 1H), 8.65 (dd, J = 4.8, 1.5 Hz, 1H), 7.98−7.95 (m, 1H), 7.85 (t, J = 1.6 Hz, 1H), 7.78 (t, J = 1.6 Hz, 1H), 7.69−7.67 (m, 3H), 7.52−7.49 (m, 2H), 7.44−7.40 (m, 3H), 7.35 (dd, J = 5.1, 1.0 Hz, 1H), 7.14 (dd, J = 5.1, 3.6 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 149.0, 148.5, 143.8, 143.0, 140.6, 139.3, 136.5, 135.9, 134.7,

129.1, 128.3, 128.0, 127.4, 125.5, 125.4, 124.7, 123.9, 123.8, 123.7. IR (KBr) ν 1595, 1395, 1023, 876, 806, 760, 699. HRMS (APCIorbitrap) m/z: Calc. for C21H16NS ([M + H]+) 314.0998, Found 314.0993. 4-Bromo-5′-methyl-1,1′:3′,1″-terphenyl (3zf)20 (ZCL-850) Yield. 25 mg, 39%, white solid, mp 98−99 °C, Rf = 0.45 (petroleum ether/ ethyl acetate, 20:1). 1H NMR (400 MHz, CDCl3) δ 7.63−7.61 (m, 2H), 7.58−7.56 (m, 3H), 7.52−7.49 (m, 2H), 7.47−7.43 (m, 2H), 7.41 (s, 1H), 7.38−7.35 (m, 2H), 2.48 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 142.0, 141.1, 140.6, 140.2, 139.0, 131.9, 128.9, 128.8, 127.44, 127.37, 127.3, 126.7, 123.2, 121.6, 21.6. IR (KBr) ν 2919, 1645, 1597, 1468, 1074, 1007, 824, 761, 698. HRMS (APCI-orbitrap) m/z: Calc. for C19H15Br (M+) 322.0352, Found 322.0349. Deuterium Experiment. A 25 mL Schlenk tube equipped with a stir bar was closed with a septum, evacuated, and backfilled with nitrogen. To this tube was added cyanocyclohexadiene IV-q′ (85 mg, 0.2 mmol, disolved in 2 mLof THF), followed by the addition of D2O (5 equiv) and DBU (0.2 equiv). After stirring for about 2 h at room tempreture, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to furnish the corresponding product 3q with 56% deuterium (57 mg, 71%).

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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.8b01740. 1 H and 13C NMR spectra for obtained compounds (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] ORCID

Song Ye: 0000-0002-3962-7738 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS Financial support from the National Natural Science Foundation of China (Nos 21425207, 21521002) and the Chinese Academy of Sciences is greatly acknowledged.

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REFERENCES

(1) Morrill, L. C.; Smith, A. D. Organocatalytic Lewis Base Functionalisation of Carboxylic Acids, Esters and Anhydrides via C1Ammonium or Azolium Enolates. Chem. Soc. Rev. 2014, 43, 6214. (2) Vellalath, S.; Romo, D. Asymmetric Organocatalysis: The Emerging Utility of α,β-Unsaturated Acylammonium Salts. Angew. Chem., Int. Ed. 2016, 55, 13934. (3) Bappert, E.; Muller, P.; Fu, G. C. Asymmetric [3 + 2] Annulations Catalyzed by a Planar-chiral Derivative of DMAP. Chem. Commun. 2006, 2604. (4) Vellalath, S.; Van, K. N.; Romo, D. Direct Catalytic Asymmetric Synthesis of N-Heterocycles from Commodity Acid Chlorides by Employing α,β-Unsaturated Acylammonium Salts. Angew. Chem., Int. Ed. 2013, 52, 13688. (5) (a) Robinson, E. R. T.; Fallan, C.; Simal, C.; Slawin, A. M. Z.; Smith, A. D. Anhydrides as α,β-Unsaturated Acyl Ammonium Precursors: Isothiourea-Promoted Catalytic Asymmetric Annulation Processes. Chem. Sci. 2013, 4, 2193. (b) Matviitsuk, A.; Taylor, J. E.; Cordes, D. B.; Slawin, A. M. Z.; Smith, A. D. Enantioselective Stereodivergent Nucleophile-Dependent Isothiourea-Catalysed Domino Reactions. Chem. - Eur. J. 2016, 22, 17748. (6) Fukata, Y.; Asano, K.; Matsubara, S. Facile Net Cycloaddition Approach to Optically Active 1,5-Benzothiazepines. J. Am. Chem. Soc. 2015, 137, 5320.

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DOI: 10.1021/acs.joc.8b01740 J. Org. Chem. 2018, 83, 12507−12513

Article

The Journal of Organic Chemistry (7) Liu, G.; Shirley, M. E.; Van, K. N.; McFarlin, R. L.; Romo, D. Rapid Assembly of Complex Cyclopentanes Employing Chiral, α,βUnsaturated Acylammonium Intermediates. Nat. Chem. 2013, 5, 1049. (8) (a) Abbasov, M. E.; Hudson, B. M.; Tantillo, D. J.; Romo, D. Acylammonium Salts as Dienophiles in Diels−Alder/Lactonization Organocascades. J. Am. Chem. Soc. 2014, 136, 4492. (b) Abbasov, M. E.; Hudson, B. M.; Tantillo, D. J.; Romo, D. Stereodivergent, DielsAlder-initiated Organocascades Employing α,β-Unsaturated Acylammonium Salts: Scope, Mechanism, and Application. Chem. Sci. 2017, 8, 1511. (9) Ahlemeyer, N. A.; Birman, V. B. Asymmetric Catalytic Synthesis of Thiochromenes via an Acyl Transfer-Initiated Cascade. Org. Lett. 2016, 18, 3454. (10) (a) Wan, M.; Yao, M.; Gong, J.-Y.; Yang, P.; Liu, H.; Li, A. Synthesis of the Tetracyclic Core of Chlorospermines. Chin. Chem. Lett. 2015, 26, 272. (b) Li, Y.; Zhu, S.; Li, J.; Li, A. Asymmetric Total Syntheses of Aspidodasycarpine, Lonicerine, and the Proposed Structure of Lanciferine. J. Am. Chem. Soc. 2016, 138, 3982. (c) Sun, Y.; Meng, Z.; Chen, P.; Zhang, D.; Baunach, M.; Hertweck, C.; Li, A. A Concise Total Synthesis of Sespenine, a Structurally Unusual Indole Terpenoid from Streptomyces. Org. Chem. Front. 2016, 3, 368. (d) Yang, P.; Yao, M.; Li, J.; Li, Y.; Li, A. Total Synthesis of Rubriflordilactone B. Angew. Chem., Int. Ed. 2016, 55, 6964. (11) (a) Aldeghi, M.; Malhotra, S.; Selwood, D. L.; Chan, A. W. E. Two- and Three-dimensional Rings in Drugs. Chem. Biol. Drug Des. 2014, 83, 450. (b) Zhao, H.; Lu, Y.; Sheng, L.; Yuan, Z.; Wang, B.; Wang, W.; Li, Y.; Ma, C.; Wang, X.; Zhang, D.; Huang, H. Discovery of Fluorine-Containing Benzoxazinyl-oxazolidinones for the Treatment of Multidrug Resistant Tuberculosis. ACS Med. Chem. Lett. 2017, 8, 533. (12) Shirota, Y. Photo- and Electroactive Amorphous Molecular MaterialsMolecular Design, Syntheses, Reactions, Properties, and Applications. J. Mater. Chem. 2005, 15, 75. (13) (a) Uribe-Romo, F. J.; Doonan, C. J.; Furukawa, H.; Oisaki, K.; Yaghi, O. M. Crystalline Covalent Organic Frameworks with Hydrazone Linkages. J. Am. Chem. Soc. 2011, 133, 11478. (b) Sakaushi, K.; Antonietti, M. Carbon- and Nitrogen-Based Organic Frameworks. Acc. Chem. Res. 2015, 48, 1591. (c) Yang, B.; Björk, J.; Lin, H.; Zhang, X.; Zhang, H.; Li, Y.; Fan, J.; Li, Q.; Chi, L. Synthesis of Surface Covalent Organic Frameworks via Dimerization and Cyclotrimerization of Acetyls. J. Am. Chem. Soc. 2015, 137, 4904. (14) Vishnoi, P.; Walawalkar, M. G.; Sen, S.; Datta, A.; Patwari, G. N.; Murugavel, R. Selective Fluorescence Sensing of Polynitroaromatic Explosives Using Triaminophenylbenzene Scaffolds. Phys. Chem. Chem. Phys. 2014, 16, 10651. (15) (a) Ruiter, G. d.; Thompson, N. B.; Lionetti, D.; Agapie, T. Nitric Oxide Activation by Distal Redox Modulation in Tetranuclear Iron Nitrosyl Complexes. J. Am. Chem. Soc. 2015, 137, 14094. (b) Ruiter, G. d.; Thompson, N. B.; Takase, M. K.; Agapie, T. Intramolecular C−H and C−F Bond Oxygenation Mediated by a Putative Terminal Oxo Species in Tetranuclear Iron Complexes. J. Am. Chem. Soc. 2016, 138, 1486. (16) (a) Zhu, T.; Zheng, P.; Mou, C.; Yang, S.; Song, B.-A.; Chi, Y. R. Benzene Construction via Organocatalytic Formal [3 + 3] Cycloaddition Reaction. Nat. Commun. 2014, 5, 5027. (b) Zhu, T.; Mou, C.; Li, B.; Smetankova, M.; Song, B.-A.; Chi, Y. R. NHeterocyclic Carbene-Catalyzed δ-Carbon LUMO Activation of Unsaturated Aldehydes. J. Am. Chem. Soc. 2015, 137, 5658. (c) Wu, J. C.; Mou, C. L.; Chi, Y. R. Construction of Multi-Substituted Benzenes via NHC-Catalyzed Reactions of Carboxylic Esters. Chin. J. Chem. 2018, 36, 333. (17) (a) Candish, L.; Levens, A.; Lupton, D. W. N-Heterocyclic Carbene Catalysed Redox Isomerisation of Esters to Functionalised Benzaldehydes. Chem. Sci. 2015, 6, 2366. (b) Nakano, Y.; Lupton, D. W. Enantioselective N-Heterocyclic Carbene Catalysis by the Umpolung of α,β-Unsaturated Ketones. Angew. Chem., Int. Ed. 2016, 55, 3135.

(18) Liu, J.; Das, D. K.; Zhang, G.; Yang, S.; Zhang, H.; Fang, X. NHeterocyclic Carbene-Catalyzed Umpolung of β,γ-Unsaturated 1,2Diketones. Org. Lett. 2018, 20, 64. (19) (a) Jia, Q.; Wang, J. N-Heterocyclic Carbene-Catalyzed Convenient Benzonitrile Assembly. Org. Lett. 2016, 18, 2212. (b) Zhang, C.-L.; Gao, Z.-H.; Liang, Z.-Q.; Ye, S. N-Heterocyclic Carbene-Catalyzed Synthesis of Multi-Substituted Benzenes from Enals and α-Cyano-β-methylenones. Adv. Synth. Catal. 2016, 358, 2862. (20) Zhang, C.-L.; Ye, S. N-Heterocyclic Carbene-Catalyzed Construction of 1,3,5-Trisubstituted Benzenes from Bromoenals and α-Cyano-β-methylenones. Org. Lett. 2016, 18, 6408. (21) (a) Larrivée-Aboussafy, C.; Jones, B. P.; Price, K. E.; Hardink, M. A.; McLaughlin, R. W.; Lillie, B. M.; Hawkins, J. M.; Vaidyanathan, R. DBU Catalysis of N,N′-CarbonyldiimidazoleMediated Amidations. Org. Lett. 2010, 12, 324. (b) Heller, S. T.; Schultz, E. E.; Sarpong, R. Chemoselective N-Acylation of Indoles and Oxazolidinones with Carbonylazoles. Angew. Chem., Int. Ed. 2012, 51, 8304. (22) (a) Aurelio, L.; Valant, C.; Flynn, B. L.; Sexton, P. M.; Christopoulos, A.; Scammells, P. J. Allosteric Modulators of the Adenosine A1 Receptor: Synthesis and Pharmacological Evaluation of 4-Substituted 2-Amino-3-benzoylthiophenes. J. Med. Chem. 2009, 52, 4543. (b) Gu, Y.; Hu, P.; Ni, C.; Tong, X. Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β′-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine. J. Am. Chem. Soc. 2015, 137, 6400. (23) Kumar, A.; Dixit, M.; Singh, S. P.; Raghunandan, R.; Maulik, P. R.; Goel, A. Reusable Resin Amberlyst 15 Catalyzed New Convenient Protocol for Accessing Arylated Benzene Scaffolds. Tetrahedron Lett. 2009, 50, 4335. (24) Hu, Z.; Liu, J.; Li, G.; Dong, Z.; Li, W. Synthesis of Asymmetric Triarylbenzenes by Using SOCl2-C2H5OH Reagent. J. Chin. Chem. Soc. 2004, 51, 581. (25) Kotha, S.; Kashinath, D.; Lahiri, K.; Sunoj, R. B. Synthesis of C3-Symmetric Nano-Sized Polyaromatic Compounds by Trimerization and Suzuki−Miyaura Cross-Coupling Reactions. Eur. J. Org. Chem. 2004, 2004, 4003. (26) Melandri, D.; Montevecchi, P. C.; Navacchia, M. L. Thiol Radical Addition to Alkynes. Sulfanyl Radical Addition and Hydrogen Atom Abstraction Relative Reaction Rates. Tetrahedron 1999, 55, 12227.

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