Copper-Catalyzed Radical Reductive Arylation of Styrenes with Aryl Iodides Mediated by Zinc in Water

Article abstract of DOI:10.1021/acs.joc.8b00278

A copper/aniline catalyst system enables the radical arylation of styrenes using aryl iodides mediated by zinc in water. This transformation provides an efficient synthetic methodology for the convenient synthesis of diarylethane.

Full text of DOI:10.1021/acs.joc.8b00278

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Article
Copper-Catalyzed Radical Reductive Arylation of
Styrenes with Aryl Iodides Mediated by Zinc in Water
Feng Zhou, Xiaoyun Hu, Wanying Zhang, and Chao-Jun Li
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00278 • Publication Date (Web): 27 Apr 2018
Downloaded from http://pubs.acs.org on April 27, 2018
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CopperꢀCatalyzed Radical Reductive Arylation of Styrenes with Aryl
Iodides Mediated by Zinc in Water
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Feng Zhou [a,+], Xiaoyun Hu [a,b,+], Wanying Zhang[a] and ChaoꢀJun Li[a] *
aDepartment of Chemistry and FQRNT Center for Green Chemistry and Catalysis, McGill
University, 801 Sherbrooke Street West, Montreal, Quebec, H3A 0B8, Canada. [+]These authors
contributed equally to this work. *cj.li@mcgill.ca
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bCollege of Chemistry and Materials Science, SouthꢀCentral University for Nationalities, Wuhan,
430074, PR China
TOC Table
Abstract
A copper/aniline catalyst system enables the radical arylation of styrenes using aryl iodides
mediated by zinc in water. This transformation provides an efficient synthetic methodology for
the convenient synthesis of diarylethane.
INTRODUCTION
Environmental concerns and resource depletion have given rise to the increased attentions in
developing novel chemistry that could lead to more sustainable chemical syntheses,1 among which is
the development of organic reactions by using water as solvent.2 Many types of reactions that are
traditionally conducted exclusively in organic solvents can now be carried out in water with
additional interesting features.2cꢀe, 3 In particular, there has been considerable progress in the
development of various transitionꢀmetalꢀcatalyzed reactions in water, 2a, 2b, 2e, 4 among which one
of the most attractive and practical studies is the radical chemistry catalyzed by transition
metals.5
6
Radical reactions are generally triggered by either the irradiation of a radical initiator (e.g.
benzoyl peroxide or AIBN) or by means of SET (singleꢀelectron transfer) between the lowꢀ
valent transition metal (or transition metal complex) and organic molecules, typically alkyl
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halides.7 On one hand, since being chargeꢀneutral, these radical reactions not only can tolerate
aqueous conditions but also are particularly effective in water, as have been shown by Oshima8
and others.9 Furthermore, the resulting radicals might also be incorporated into the formation of
metalꢀcarbon bond via redox process involved in catalytic cycle. As the exemplary reactions that
combine the transitionꢀmetal catalysis and radical reaction, the atomꢀtransfer radical
polymerization (ATRP)10 and atomꢀtransfer radical addition (ATRA)11 are among the most
widely used and recognized transformations (Scheme 1, a).
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Despite myriad reports regarding the efficient generation of alkyl radical species from the
reaction of copper salt with an alkyl halides,10b, 12 including ATRP and ATRA, the generation of
aryl radical from aryl halide has been relatively less investigated13 except for the tin hydrideꢀ
mediated method14 and photoꢀinduced SET,15 largely due to the highꢀdissociationꢀenergy of a
nonꢀactivated C(sp2)ꢀhalogen bond. To the best of our knowledge, there has been no report on
the copperꢀcatalyzed intermolecular radical arylation of olefin with aryl halides,16 especially in
water. Therefore, it is highly desirable to develop the radical alkene arylation, analogous to the
ATRP alkene alkylation process, and explore its application. Herein, we report the first
copper/anilineꢀcatalyzed radical reductive arylation of styrenes17 mediated by zinc in water
(Scheme 1, b).
Scheme 1. a) Cu/ligandꢀcatalyzed atomꢀtransferꢀradicalꢀpolymerization. b) This work,
Cu/anilineꢀcatalyzed radical reductive arylation of styrenes with aryl iodides mediated by zinc in
water
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RESULTS AND DISCUSSION
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Our initial studies were focused on the copperꢀcatalyzed reaction of iodobenzene (1a) and 4ꢀ
chlorostyrene (2a). We were delighted to find that a small amount of desired product 3aa was
observed when the reaction was treated with IiPrSꢀCuCl/zinc in 1% of BrijC10 (Table 1, entry 1).
The yield was further increased to 20% with 3.9 equiv of Zn (Table 1, entry 2). When 10 mol%
of catalyst complex IiPrSꢀCuCl was used, the reaction afforded 3aa in 30% yield (Table 1, entry
3). Switching catalyst from IiPrSꢀCuCl to Cu(acac)2 resulted in lower yields with BrijC10
(polyoxyethylene (10) cetyl ether) and CTAS (cetyltrimethylammonium hydrogensulfate) as
surfactants 18 respectively (Table 1, entries 4 and 5). Then a series of ligands were investigated,
and interestingly, a significant amount of product 3aa was obtained with pꢀanisidine being the
ligand (Table 1, entries 6ꢀ9). The even more electronꢀrich 3, 4ꢀdimethoxyaniline proved to be a
better ligand, providing 3aa in 58% yield after 26 h (Table 1, entry 10). Conducting the reaction
with the ratio of catalyst and ligand tuned from 1/1 to 1/2 further improved the yield to 64%
(Table 1, entries 11ꢀ13). It is worth noting that the reaction could be carried out at room
temperature under extended reaction time (36 h) without significantly compromising the yield
(Table 1, entry 14). Subsequently, electronꢀrich ligands 3, 4ꢀ(methylenedioxy)aniline and 3, 4, 5ꢀ
trimethoxyaniline were subjected to further evaluation (Table 1, entries 15 and 16), neither of
which afforded better yields than 3,4ꢀdimethoxyaniline. Finally, 63% yield of the corresponding
product was obtained with water as the sole solvent (Table 1, entry 17).
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Table 1. Conditions for Cuꢀcatalyzed and zincꢀmediated arylation of styrene in water a
Entry
Cat.
(mol%)
Zinc
(equiv)
Ligand
(mol%)
Solvent
(surfactant
1%)
Time
(h)
Yield
(%)b
1
2
3
4
5
6
7
8
IiPrSꢀCuCl (5)
IiPrSꢀCuCl (5)
IiPrSꢀCuCl (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
1.2
3.9
3.9
3.9
3.9
3.9
3.9
3.9
BrijC10
BrijC10
BrijC10
BrijC10
CTAS
CTAS
CTAS
CTAS
12
12
12
12
12
16
16
16
5
20
30(27)
5
13
17
ꢀ
ꢀ
DMAP (10)
2,2’ꢀbipyridine (10)
2,3ꢀdiaminopyridine (10)
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Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (5)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
Cu(acac)2 (10)
3.9
3.9
3.9
3.9
3.9
3.9
3.9
3.9
3.9
pꢀanisidine (10)
CTAS
CTAS
CTAS
CTAS
CTAS
CTAS
CTAS
CTAS
H2O
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26
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36
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49
58
64(59)
61(63)
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63
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14c
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3,4-dimethoxyaniline (10)
3,4-dimethoxyaniline (10)
3,4-dimethoxyaniline (20)
3,4-dimethoxyaniline (20)
3,4-dimethoxyaniline (20)
3,4ꢀ(methylenedioxy)aniline (20)
3,4,5-trimethoxyaniline (20)
3,4-dimethoxyaniline (20)
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a Reaction conditions: 1a (0.60 mmol), 2a (0.20 mmol), Zn dust, surfactant (1%) in H2O (W/V) (0.5 mL),
o
b
1
70 C. Yields were determined by H NMR analysis with 1,3,5ꢀtrimethoxybenzene as an internal
c
standard. The reaction was conducted at room temperature. Isolated yields in brackets. BrijC10 =
polyoxyethylene (10) cetyl ether. CTAS = cetyltrimethylammonium hydrogensulfate.
With the optimized reaction conditions in hand, the scope of this arylation chemistry was then
investigated and the results were shown in Table 2. The reactions of iodobenzene (1a) and 3ꢀ
methyliodobenzene (1b) proceeded smoothly to give the corresponding products in 63% and 56%
yields, respectively (Table 2, 3aa and 3ba). Substrates 1cꢀe bearing electronꢀdonating groups
could also react successfully to provide the products in yields ranging from 36ꢀ45% (Table 2,
3caꢀ3ea), among which the lower yield of the substrate bearing oꢀmethoxyl (1e) is probably due
to both electronic and steric effects. Interestingly, in the case of 4ꢀfluoroiodobenzene (1f), the
reaction was completed in 16 h and the yield declined dramatically to 34% (Table 2, 3fa). The
reactions of 1g bearing a strong electronꢀwithdrawing group trifluoromethyl group with styrenes
2aꢀc afforded the arylated products in good to excellent yields (Table 2, 3gaꢀ3gc). Surprisingly,
when heterocyclic substrates, 2ꢀbromopyridine (1h) and 2ꢀiodothiophene (1i), were subjected to
the standard conditions, only trace amounts of products were detected, along with the
corresponding dehalogenated heterocycles as major byproducts (Table 2, 3ha and 3ia). Then the
arylation on styrene 2a gave rise to the corresponding product in 63% yield (Table 2, 3ab).
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Subjecting 4ꢀtertꢀbutylstyrene (2c) to the standard conditions, the reactions of 1a and 1f gave the
corresponding arylation products in 72% and 34% yields, respectively (Table 2, 3ac and 3fc).
Furthermore, electronꢀrich styrene 2d, bearing 3, 4ꢀdimethoxyl groups, reacted smoothly with
iodobenzene (1a) and 3ꢀtrifluoroiodobenzene (1g) to furnish the corresponding products in
moderate yields (Table 2, 3ad and 3gd). Then the standard reaction was applied to 4ꢀ
trifluorostyrene (2e) and a series of iodoarenes bearing electronꢀdonating and electronꢀ
withdrawing groups, affording the desired products in 34ꢀ62% yields (3aeꢀ3ce and 3fe). Notably,
4ꢀphenylstyrene (2f) was also accommodated, providing the corresponding product 3af in 40%
yield, albeit with a slight modification of the reaction conditions. Additionally, the reaction
protocol was also successfully applied to transꢀβꢀmethylstyrene, giving rise to desired product in
27% yield (Table 2, 3ag).
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Table 2. Cuꢀcatalyzed and zincꢀmediated arylation of styrenes in water a, b
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a Reaction conditions: 1 (0.40 mmol), 2 (0.20 mmol), Cu(acac)2 (10 mol%), 3, 4ꢀdimethoxyaniline (20
mmol%), Zn dust (0.78 mmol), H2O (0.5 mL) at 70 o for 16 h. b All yields are those for isolated products. c
d
<10% yield was obtained when bromobenzene was used. The hydrodehalogenation of the 2ꢀ
e
bromopyridine and 2ꢀiodothiophene gave the corresponding heterocycles as major byproducts. 4,4’ꢀtBuꢀ
bpy (20 mol%) was added as ligand and H2O/DMF(10/1, 1.0 mL) as solvent
This robust catalytic system prompted us to further examine the feasibility of its scalingꢀup.
Subsequently, the reaction between iodobenzene (1a) and 4ꢀchlorostyrene (2a) was scaled up to
o
10.0 mmol. After performing the reaction in water as sole solvent at 70 C for 16 h, an isolated
yield of 52% was obtained (Scheme 2).
Scheme 2. Gramꢀscale of the Cuꢀcatalyzed and Znꢀmediated arylation of styrene 2a in water
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I
Cu(acac) (10 mol%)/
ligand (20 mol%)
Zn dust (3.9 equiv)
70 oC/H2O/16 h
2
+
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Cl
Cl
1a
20 mmol
2a
3aa
MeO
NH2
1.12 g, 52%
10 mmol
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MeO
ligand
Inspired by the mechanism of ATRP10c and also based on our previous work,19 we tentatively
proposed the mechanism for this copperꢀcatalyzed arylation of styrenes using aryl halides
(Scheme 3). We speculated that a singleꢀelectronꢀtransfer from zinc or zinc/Cu (as in the case of
zincꢀcopper couple) to aryl iodide would generate an aryl radical anion I, which could be rapidly
trapped by the active catalyst CuIL (II) (formed in situ from the coordination of a suitable ligand
to Cu salt) to afford an organocopper species III. The reactivity of species III is crucial and
could be tuned through the properties of the coordinated ligand. More specifically, this
intermediate should be stable enough to accommodate the electrons received from the radical anion
I via delocalization as well as survive the hydrolysis in aqueous media. On the other hand, the
Wurtzꢀtype homoꢀcoupling of aryl halides needs to be inhibited by preventing the formation of
the diarylcopper species through introducing modest steric hindrance into the ligand. If the rate
of complex III formation matches the rates of the ensuing steps, the πꢀcoordination of the
carbonꢀcarbon double bond to the resulting Cu (II) center would afford a transient intermediate
(IV), which was followed by the insertion of carbonꢀcarbon double bond into carbonꢀcopper
bond to provide intermediate V. Subsequently, zincꢀmediated reduction of the reactive complex
V would furnish intermediate VI, which upon protonation by water releases the product and
regenerates the active catalyst Cu(I)L to complete the catalytic cycle. Alternatively, hydrolysis of
intermediate V would deliver the arylated product and give rise to the copper species VII that
could be reduced by zinc to regenerate the active Cu(I)L catalyst.
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Scheme 3. Plausible mechanism of Cuꢀcatalyzed arylation of styrenes mediated by zinc in water
On the basis of our previous work, we tentatively proposed that the role of the electronꢀrich
aniline not only participates in the formation of active ligand, but also prevents the diarylcopper
formation that accounts for the homoꢀcoupling of aryl iodide either by direct coordination to
active Cu catalyst or through the steric hindrance surrounding the Cu catalytic centre20 (Scheme
4).
Scheme 4. Possible catalytic active Cuꢀcomplex
CONCLUSION
In summary, we have demonstrated the unprecedented copperꢀcatalyzed radical arylations
of styrenes mediated by zinc in water. This simple and mild transformation is scalable as well.
This method provides a convenient route for the preparation diarylethanes, which complements
the twoꢀsteps reductive Heck reaction. Efforts to extend this catalytic protocol to increase its
efficiency, broaden its scope, and further understand the mechanism are in progress in our
laboratory.
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EXPERIMENTAL SECTION
1. General Information
All commercially available compounds were purchased from SigmaꢀAldrich, Strem and
Acros, and were used as received. Unless otherwise noted, all reagents were weighed and
handled in air. NMR spectra were recorded on Varian Mercury plusꢀ300 spectrometer, Varian
MERCURY plusꢀ400 spectrometer, and Varian VNMRS 500 spectrometer with proton
resonances at 300/400/500 MHz and carbon resonances at 75/100/125 MHz, respectively.
Chemical shifts are reported in parts per million (ppm). The solvent residual peaks, e.g., of
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chloroform (CDCl3: δ 7.26 ppm for HꢀNMR and δ 77.26 ppm for 13CꢀNMR), were used as
references. Data are reported as following: chemical shift, multiplicity (s = singlet, d = doublet,
dd = doublet of doublets, t = triplet, q = quartet, m = multiplet, br = broad signal) and integration.
Flash column chromatography was performed with Biotage Isolera with cartridge. Analytical
thin layer chromatography (TLC) was performed using Merck silica gel 60 F254 preꢀcoated
plates (0.25 mm). GCꢀMS were recorded on an Agilent 5975 GCꢀMS instrument (EI). HRMS
measurements were conducted through atmospheric pressure chemical ionization (APCI) or
electroꢀspraying ionization (ESI), and were performed at McGill University on a Thermoꢀ
Scientific Exactive Orbitrap. Zinc dust was treated by the standard procedure (Armarego, W. L.
F.; Chai, C. L. L. Purification of Laboratory Chemicals; Elsevier Science, 2003) and other
chemicals were used as received. The complex IiPrSꢀCuCl was prepared according to literature.21
2. Typical Procedure for Copper-Catalyzed Radical Reductive Arylations of Styrenes
with Aryl Iodides Mediated by Zinc in Water
To a microwave tube were charged with Cu(acac)2 (0.02 mmol, 5.2 mg), 3,4ꢀ
dimethoxyaniline (0.04 mmol, 6.1 mg), zinc dust (0.78 mmol, 50.7 mg). [Organohalide (0.40
mmol) or styrene (0.20 mmol) was added at this point if the compound is a solid]. Then the
solvent, CTAS in H2O (1% w/v) or deionized water (0.5 mL), was injected via syringe, followed
by the addition of iodobenzene (1a, 0.40 mmol, 81.6 mg, 45.0 ꢀL) and 4ꢀchlorostyrene (2a, 0.20
o
mmol, 27.7 mg, 24.0 ꢀL). The tube was then sealed. The reaction mixture was heated to 70 C
and stirred vigorously (1400 rpm) for 16 h. After cooling to room temperature, the mixture was
diluted with EtOAc (8 mL) and filtered through a short silica gel pad. The filter cake was further
flushed with EtOAc (6 x 4 mL). The combined solution was concentrated under vacuum, and the
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residue was purified by flash chromatography on silica gel to afford the analytically pure product
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3aa (27.3 mg, 63%).
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Preparation of 1% of CTAS/H2O solution: A 20 mL vial was charged with CTAS
(cetyltrimethylammonium hydrogensulfate) (100 mg). Then degassed water (10 mL) was added
via syringe. The mixture was placed in a sonicator and oscillated for 10 mins. Occasional
vigorous shaking was essential for the formation of wellꢀdistributed emulsion. The emulsion was
stored under argon. The emulsion (1% w/v, 0.5 mL) was shaken vigorously before being injected
into the reaction tube.
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3. The Gram-Scale Synthesis
To a roundꢀbottom flask was charged with Cu(acac)2 (1.00 mmol, 0.260 g), 3,4ꢀ
dimethoxyaniline (2.00 mmol, 0.305 g) and zinc dust (39.0 mmol, 2.54 g). The flask was
plugged with a rubber septum. Deionized water (25.0 mL) was injected via syringe, followed by
the addition of iodobenzene (1a, 20.0 mmol, 4.08 g, 2.30 mL) and 4ꢀchlorostyrene (2a, 10.0
o
mmol, 1.39 g, 1.20 mL). The reaction mixture was heated to 70 C and stirred vigorously (1200
rpm) for 16 h. After cooling to room temperature, water (15 mL) and EtOAc (15 mL) were
added. The organic layer was separated and the aqueous phase was extracted with EtOAc (3 x 25
mL). The combined organic layers were dried over MgSO4, filtered and concentrated under
reduced pressure. The residue was purified by flash chromatography on silica gel to afford the
product 3aa (1.12 g, 52%).
4. Characterizations of Products
1
13
For the known compounds, H NMR and C NMR data and spectra, as well as MS data are
reported. Full characterization data are provided for new compounds.
1
1-chloro-4-phenethylbenzene (3aa)22: 27.3 mg, 63% yield, colorless oil; H NMR (500 MHz,
CDCl3) δ 7.29 (t, J = 7.4 Hz, 2H), 7.25ꢀ7.19 (m, 3H), 7.16 (d, J = 8.2 Hz, 2H), 7.09 (d, J = 8.4
Hz, 2H), 2.90 (s, 4H). 13C NMR (125 MHz, CDCl3) δ 141.5, 140.3, 131.9, 130.1, 128.7, 128.63,
128.61, 126.3, 38.0, 37.4. MS (EI) m/z: 216.1.
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1-(4-chlorophenethyl)-3-methylbenzene (3ba): 25.8 mg, 56% yield, colorless oil; H NMR
(500 MHz, CDCl3) δ 7.23 (d, J = 8.3 Hz, 2H), 7.18 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 8.4 Hz, 2H),
7.03ꢀ6.96 (m, 4H), 2.33 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 141.5, 140.3, 131.9, 130.1, 128.7,
128.63, 128.61, 126.3, 38.0, 37.4. HRMS calcd for C15H16Cl [M+H] + 231.0935, found 231.0944.
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1-chloro-4-(4-methoxyphenethyl)benzene (3ca) : 19.2 mg, 39% yield, colorless oil; 1H NMR
(500 MHz, CDCl3) δ 7.24 (d, J = 8.4 Hz, 2H), 7.08ꢀ7.05 (m, 4H), 6.82 (d, J = 8.6 Hz, 2H), 3.79
(s, 3H), 2.86ꢀ2.84 (m, 4H). 13C NMR (125 MHz, CDCl3) δ 158.1, 140.4, 133.6, 131.8, 130.1,
129.6, 128.6, 114.0, 55.5, 37.7, 37.1. MS (EI) m/z: 246.1.
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1-chloro-4-(3-methoxyphenethyl)benzene (3da) : 22.1 mg, 45% yield, colorless oil; 1H NMR
(500 MHz, CDCl3) δ 7.25ꢀ7.18 (m,3H), 7.09 (d, J = 8.4 Hz, 2H), 6.75 (dd, J = 7.9, 2.1 Hz, 2H),
6.70ꢀ6.69 (m, 1H), 3.78 (s, 3H), 2.86ꢀ2.81 (m, 4H). 13C NMR (125 MHz, CDCl3) δ 159.9, 143.1,
140.3, 131.9, 130.1, 129.6, 128.6, 121.1, 114.5, 111.6, 55.4, 38.0, 37.3. MS (EI) m/z: 246.1.
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1-(4-chlorophenethyl)-2-methoxybenzene (3ea) : 17.7 mg, 36% yield, colorless oil; 1H NMR
(500 MHz, CDCl3) δ 7.23ꢀ7.17 (m, 3H), 7.11ꢀ7.05 (m, 3H), 6.86 (t, J = 7.1 Hz, 2H), 3.82 (s, 3H),
2.89ꢀ2.83 (m, 4H). 13C NMR (125 MHz, CDCl3) δ 157.7, 141.1, 131.6, 130.1, 130.1, 130.0,
128.5, 127.5, 120.6, 110.5, 55.5, 35.8, 32.6. MS (EI) m/z: 246.1.
1-(4-chlorophenethyl)-3-(trifluoromethyl)benzene (3fa) 25: 15.9 mg, 34% yield, white solid;
1H NMR (500 MHz, CDCl3) δ 7.23 (d, J = 8.4 Hz, 2H), 7.09ꢀ7.04 (m, 4H), 6.95 (t, J = 8.7 Hz,
2H), 2.86 (s, 4H). 13C NMR (125 MHz, CDCl3) δ 162.6, 160.6, 140.0, 137.0 (d, J = 3.2 Hz),
130.0, 130.1 (d, J = 7.2 Hz), 128.7, 115.4, 115.3, 37.5 (d, J = 0.7 Hz), 37.1. MS (EI) m/z: 234.1.
1-(4-chlorophenethyl)-3-(trifluoromethyl)benzene (3ga): 37.5 mg, 66% yield, colorless oil; 1H
NMR (500 MHz, CDCl3) δ 7.46 (d, J = 7.7 Hz, 1H), 7.41ꢀ7.37 (m, 2H), 7.30 (d, J = 7.6 Hz, 1H),
7.26ꢀ7.23 (m, 2H), 7.07 (d, J = 8.4 Hz, 2H), 2.98ꢀ2.94 (m, 2H), 2.92ꢀ2.89 (m, 2H). 13C NMR
(125 MHz, CDCl3) δ 142.3, 139.6, 132.2, 130.9 (q, J = 32.0 Hz), 130.0, 129.0, 128.8, 125.4 (q, J
= 3.8 Hz), 124.4 (q, J = 271.3 Hz), 123.2 (q, J = 3.9 Hz), 37.8, 31.2. HR MS calcd for
C15H13ClF3 [M+H] + 285.0652, found 285.0645.
1-phenethyl-3-(trifluoromethyl)benzene (3gb) 26: 41.0 mg, 82% yield, colorless oil; H NMR
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(500 MHz, CDCl3) δ 7.47ꢀ7.28 (m, 6H), 7.23ꢀ7.16 (m, 3H), 3.00ꢀ2.93 (m, 4H). C NMR (125
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MHz, CDCl3) δ 142.8, 141.3, 132.2, 130.8 (q, J = 30 Hz), 128.9, 128.7, 126.4, 124.5 (q, J =
271.3 Hz), 125.4 (q, J = 3.8 Hz), 123.1 (q, J = 3.9 Hz), 38.0, 37.9. MS (EI) m/z: 250.1.
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1-(4-(tert-butyl)phenethyl)-3-(trifluoromethyl)benzene (3gc): 39.2 mg, 64% yield, yellow oil;
1H NMR (500 MHz, CDCl3) δ 7.48ꢀ7.33 (m, 6H), 7.13 (d, J = 7.8 Hz, 2H), 3.00ꢀ2.97 (m, 2H),
2.94ꢀ2.90 (m, 2H), 1.34 (s, 9H). 13C NMR (125 MHz, CDCl3) δ 149.3, 143.0, 138.2, 132.1, 130.8
(q, J = 31.9 Hz), 128.9, 128.3, 125.6, 124.5 (q, J = 270 Hz), 125.5 (q, J = 3.8 Hz), 123.0 (q, J =
3.8 Hz), 38.0, 37.4, 34.6, 31.6. HR MS calcd for C19H20F3 [MꢀH] + 305.1522, found 305.1520.
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1,2-diphenylethane (3ab) : 22.9 mg, 63% yield, colorless oil. H NMR (500 MHz, CDCl3) δ
7.30ꢀ7.27 (m, 4H), 7.21ꢀ7.18 (m, 6H), 2.93 (s, 4H). 13C NMR (125 MHz, CDCl3) δ 142.0, 128.7,
128.6, 126.2, 38.2. MS (EI) m/z: 182.1.
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1-(tert-butyl)-4-phenethylbenzene (3ac) 28: 34.3 mg, 72% yield, yellow oil; H NMR (500
MHz, CDCl3) δ 7.34ꢀ7.29 (m, 4H), 7.24−7.16 (m, 5H), 2.94−2.91 (m, 4H), 1.33 (s, 9H). 13C
NMR (125 MHz, CDCl3) δ 149.0, 142.3, 139.1, 128.6, 128.6, 128.3, 126.1, 125.5, 38.2, 37.7,
34.6, 31.7. MS (EI) m/z: 238.1
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1-(tert-butyl)-4-(4-fluorophenethyl)benzene (3fc): 17.4 mg, 34% yield, white solid; H NMR
(500 MHz, CDCl3) δ 7.33 (d, J = 8.1 Hz, 2H), 7.16ꢀ7.12 (m, 4H), 6.97 (t, J = 8.7 Hz, 2H), 2.89ꢀ
2.88 (m, 4H), 1.33 (s, 9H). 13C NMR (125 MHz, CDCl3) δ 162.5, 160.6, 149.1, 138.7, 137.8 (d, J
= 3.2 Hz), 130.0 (d, J = 7.8 Hz), 128.3, 125.5, 115.3, 115.2. MS (EI) m/z: 256.1. HRMS calcd
for C18H20F[MꢀH] + 255.1544, found 255.1531.
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1,2-dimethoxy-4-phenethylbenzene (3ad) 29: 26.1 mg, 54% yield, yellow oil; H NMR (500
MHz, CDCl3) δ 7.30ꢀ7.27 (m, 2H), 7.21−7.17 (m, 3H), 6.80ꢀ6.64 (m,3H), 3.86 (s, 3H), 3.83 (s,
3H), 2.93ꢀ2.85 (m, 4H). 13C NMR (125 MHz, CDCl3) δ 148.9, 147.5, 140.0, 134.6, 128.8, 128.5,
126.1, 120.5, 112.1, 111.4, 56.2, 56.0, 38.4, 37.8. MS (EI) m/z: 242.1
1,2-dimethoxy-4-(3-(trifluoromethyl)phenethyl)benzene (3gd): 34.1 mg, 55% yield, yellow
oil; 1H NMR (500 MHz, CDCl3) δ 7.46ꢀ7.31 (m, 4H), 6.79 (d, J = 8.1 Hz, 1H), 6.70 (dd, J = 8.1,
2.0 Hz, 1H), 6.63 (d, J = 1.9 Hz, 1H), 3.86 (s, 3H), 3.83 (s, 3H), 2.98ꢀ2.95 (m, 2H), 2.90ꢀ2.86 (m,
13
2H). C NMR (125 MHz, CDCl3) δ 149.0, 147.6, 142.8, 133.9, 132.3, 132.2, 130.8 (q, J = 31.9
Hz), 125.5 (q, J = 3.7 Hz), 124.5 (q, J = 270 Hz), 123.0 (q, J = 3.8 Hz), 112.1, 111.5, 56.2, 56.0,
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38.2, 37.5. MS (EI) m/z: 310.1. HR MS calcd for C17H18F3O2 [M+H] 311.1253, found
311.1257.
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1-phenethyl-4-(trifluoromethyl)benzene (3ae) 30: 31.0 mg, 62% yield, yellow oil; H NMR
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(500 MHz, CDCl3) δ 7.53 (d, J = 8.0 Hz, 2H), 7.31−7.28 (m, 4H), 7.23ꢀ7.16 (m, 3H), 3.01ꢀ2.92
(m, 4H). 13C NMR (125 MHz, CDCl3) δ 146.0, 141.3, 129.0, 128.7, 128.3 (q, J = 65 Hz), 126.6
(q, J = 270 Hz), 126.4, 125.5 (q, J = 3.8 Hz), 37.9, 37.8. MS (EI) m/z: 250.1
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1-methyl-3-(4-(trifluoromethyl)phenethyl)benzene (3be): 24.8 mg, 47% yield, yellow oil; H
NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.1 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.18 (t, J = 7.5 Hz,
1H), 7.03ꢀ6.96 (m, 3H), 2.98ꢀ2.95 (m, 2H), 2.90ꢀ2.87 (m, 2H), 2.33 (s, 3H). 13C NMR (125 MHz,
CDCl3) δ 146.1, 141.3, 138.3, 129.5, 129.0, 128.6, 128.4 (q, J = 31 Hz), 127.1, 125.7 (q, J = 270
Hz), 125.6, 125.5 (q, J = 3.7 Hz), 38.0, 37.7, 21.6. HRMS calcd for C16H15F3(M+) 264.1125,
found 264.1121.
1-methoxy-4-(4-(trifluoromethyl)phenethyl)benzene (3ce): 19.1 mg, 34% yield, yellow oil; 1H
NMR (500 MHz, CDCl3) δ 7.52 (d, J = 8.1 Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 7.07 (d, J = 8.5 Hz,
1H), 6.83 (d, J = 8.6 Hz, 1H), 3.80 (s, 3H), 2.97–2.93 (m, 2H), 2.90–2.86 (m, 2H). 13C NMR
(125 MHz, CDCl3) δ 158.2, 146.1, 133.3, 129.6, 129.1, 128.5 (q, J = 32.3 Hz), 124.6 (q, J = 270
+
Hz), 125.4 (q, J = 3.8 Hz), 114.1, 55.5, 38.2, 36.9. HR MS calcd for C16H16F3O [M+H]
281.1253, found 281.1250.
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1-fluoro-4-(4-(trifluoromethyl)phenethyl)benzene (3fe)25: 22.5 mg, 42% yield, yellow oil; H
NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.1 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.11ꢀ7.07 (m, 2H),
13
6.99ꢀ6.94 (m,2H), 2.98−2.95 (m, 2H), 2.92ꢀ2.89 (m, 2H). C NMR (125 MHz, CDCl3) δ 162.6,
160.7, 145.7, 136.8, 130.1, 129.1, 128.7, 128.4 (q, J = 32.5 Hz), 124.6 (q, J = 270 Hz), 126.4,
125.5 (q, J = 3.8 Hz), 38.0, 36.9. MS (EI) m/z: 268.1.
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4-phenethyl-1,1'-biphenyl (3af)31: 20.6 mg, 40% yield, colorless solid; H NMR (500 MHz,
CDCl3) δ 7.60 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.36ꢀ7.26
(m, 5H), 7.25ꢀ7.15 (m, 3H), 2.97 (s, 4H). 13C NMR (125 MHz, CDCl3) δ 142.0, 141.3, 141.2,
139.1, 129.1, 129.0, 128.7, 128.6, 127.31, 127.28, 127.24, 126.20, 38.1, 37.8. MS (EI) m/z:
258.1.
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propane-1,2-diyldibenzene (3ag)32: 10.6 mg, 27% yield, colorless oil; H NMR (500 MHz,
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CDCl3) δ 7.31ꢀ7.27 (m, 2H), 7.21ꢀ7.16 (m, 5H), 7.11ꢀ7.09 (m, 2H), 3.04ꢀ2.94 (m, 2H), 2.78 (dd,
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J = 13.1, 8.1 Hz, 1H), 1.26 (d, J = 6.8 Hz, 3H). C NMR (125 MHz, CDCl3) δ 147.2, 141.1,
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129.4, 128.5, 128.3, 127.3, 126.2, 126.1, 45.3, 42.1, 21.4. MS (EI) m/z: 196.1.
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SUPPLEMENTAL INFORMATION
Copies of 1HꢀNMR and 13CꢀNMR spectra can be found in supplementary information.
AUTHOR INFORMATION
Corresponding Authors
*Eꢀmail: cj.li@mcgill.ca
Author Contributions
F.Z. and X.Y.H. contributed equally to this work
Notes:
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We are grateful to the Canada Research Chair (Tier 1) foundation (to C.ꢀJ.L.), FQRNT Center
for Green Chemistry and Catalysis, NSERC, CFI and McGill University for support of our
research. We also thank the CSC (China Scholarship Council) for a Visiting Scholar fellowship
(to X.Y.H.).
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