NHC Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions of Aryl Boronate Esters with Perfluorobenzenes

Article abstract of DOI:10.1021/acs.joc.6b01041

An efficient Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with aryl boronate esters using NHC nickel complexes as catalysts is described. The efficiencies of different boronate esters (p-tolyl-Beg, p-tolyl-Bneop, p-tolyl-Bpin, p-tolyl-B

Full text of DOI:10.1021/acs.joc.6b01041

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Note
NHC Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling
Reactions of Arylboronate Esters with Perfluorobenzenes
Jing Zhou, Johannes H. J. Berthel, Maximilian W. Kuntze-
Fechner, Alexandra Friedrich, Todd B Marder, and Udo Radius
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01041 • Publication Date (Web): 02 Jun 2016
Downloaded from http://pubs.acs.org on June 5, 2016
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NHC Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions of
Arylboronate Esters with Perfluorobenzenes
8
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Jing Zhou,a1 Johannes H. J. Berthel,a Maximilian W. Kuntze-Fechner,a Alexandra Friedrich,a
Todd B. Marder,*a and Udo Radius*a
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a Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland,
97074 Würzburg, Germany.
ABSTRACT
An efficient Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with
aryl boronate esters using NHC nickel complexes as catalysts is described. The
efficiencies of different boronate esters (p-tolyl-Beg, p-tolyl-Bneop, p-tolyl-Bpin,
p-tolyl-Bcat) and the corresponding boronic acid (p-tolyl-B(OH)2) in this type of
cross-coupling reaction was evaluated (eg
=
ethyleneglycolato; neop
=
neopentylglycolato; pin = pinacolato, cat = catecholato). Aryl-Beg was shown to be the
most reactive boronate ester among those studied. The use of CsF as an additive is
essential for an efficient reaction of hexafluorobenzene with aryl
neopentylglycolboronates.
The wide applications of pharmaceuticals, agrochemicals and materials that contain
fluoroaromatics attract scientists’ interest in the development of methods to introduce
fluorine or fluorinated building blocks into organic molecules.1 Transition
1
Present Address: College of Science, Northwest A&F University, Yangling, 712100, P. R. China;
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metal-catalyzed C-F bond activation has been well-developed in recent years.2 C-C
bond-forming processes in which polyfluorinated arenes are involved include
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5e,
7
Kumada,3 Negishi,4 Suzuki-Miyaura,5 Songashira,6 Stille,5b,
and Hiyama
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cross-coupling reactions.8 However, cross-coupling reactions of electron-deficient aryl
fluorides are usually limited in turnover numbers (if they are catalytic at all) and yields
and are often restricted to fluorinated substrates with directing groups (such as imine,
oxazoline, pyridine, nitro, keto and hydroxo groups). Among them, Suzuki-Miyaura
cross-coupling of poly- and perfluorinated arenes represents an attractive reaction due
to the mild conditions employed and the compatibility with many potential functional
groups. In previously reported5g,i,l cross-coupling reactions of poly- and perfluorinated
benzenes with boronate esters, an excess of the boronate esters is required in many
cases in order to obtain reasonable yields, and fluoride additives were often employed
to activate the boronate ester. Over the last few years, we have investigated the use of
nickel complexes stabilized by N-alkyl substituted NHCs, such as
1,3-bis(isopropyl)imidazolin-2-ylidene (iPr2Im), in stoichiometric and catalytic C-F
bond activation reactions.9 Complexes such as [Ni2(iPr2Im)4(µ-COD)] readily undergo
oxidative addition of polyfluorinated arenes at ambient temperatures and are readily
available catalysts for C-F bond transformations such as hydrodefluorination
reactions.9g We have recently reported the NHC nickel-catalyzed borylation of
polyfluorinated arenes via C-F bond activation.10 Furthermore, we reported efficient
Suzuki-Miyaura cross-coupling reaction of polyfluorinated arenes with boronic acids
using [Ni2(iPr2Im)4(µ-COD)] as a catalyst precursor.9b In light of the widespread use of
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organoboronic esters instead of organoboronic acids themselves, we decided to expand
our work and we report herein preliminary results on the Suzuki-Miyaura
cross-coupling of polyfluorinated arenes with aryl ethyleneglycolato (eg),
neopentylglycolato (neop), pinacolato (pin), and catecholato (cat) boronic acid esters.
Ohashi and Ogoshi et al. described briefly base-free Suzuki-Miyaura cross-coupling
reactions of octafluorotoluene (C7F8), hexafluorobenzene (C6F6) and fluorobenzene
(C6H5F) with 4-methoxyphenyl neopentylglycolboronate ester using our catalyst and
demonstrated that the reactions of C6F6 and C6H5F provided low yields.5l In the present
study, we optimized the conditions for the Suzuki-Miyaura cross-coupling of C6F6 with
phenyl neopentylglycolboronate (C6H5-Bneop) and compared the reactivity of different
boronate esters with perfluorinated arenes. The scope of the nickel-catalyzed
Suzuki-Miyaura coupling reactions of other fluorobenzenes was also explored.
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Initially, a variety of nickel catalysts and additives were tested for the reaction of
C6F6 1a and the boronate ester C6H5-Bneop 2a to give C6H5-C6F5 3aa (Table 1). For an
equimolar reaction (1a:2a = 1:1), the best results were obtained when 5 mol% of
dimeric [Ni2(iPr2Im)4(µ-COD)] (i.e. 10 mol% Ni) was used as a catalyst precursor, CsF
(1 eq.) as an additive and the reaction was performed in toluene at 100 °C (Table 1,
entry 1). Using these conditions, the product, C6H5-C6F5 3aa, was obtained in 71 %
yield. Each component given in Table 1, entry 1 is necessary to obtain a high yield.
Without CsF, the yield drops significantly to 17 % (Table 1, entry 2 and 3), whereas
without catalyst, no conversion was detected (Table 1, entries 4 and 5). The NHC
i
ligand Pr2Im alone is also not a catalyst for this reaction (Table 1, entry 5). Ni(II)
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precursors were not effective catalysts, while other Ni(0) complexes are much less
effective than [Ni2(iPr2Im)4(µ-COD)]. The closely related Ni(0) complex
[Ni(IMes)2],11 for example, afforded the product in only 17 % yield using the same
conditions (Table 1, entry 6). Using the Ni(II) complexes [(iPr2Im)2NiBr2]12 and
[(Me2Im)2NiI2],13 no product formation was observed (Table 1, entries 7 and 8).
NHC-stabilized nickel carbonyls14 are also ineffective for this reaction (Table 1, entries
9 and 10) as well as in situ-generated Ni(0) bis(phosphine) complexes15 (Table 1,
entries 11-13).
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The choice of base and solvent for Suzuki–Miyaura reactions is, by and large,
empirical but, in general, ethereal and aromatic hydrocarbon solvents and carbonate,
phosphate, hydroxide, and fluoride bases tend to be optimal. The influence of the
additives/bases were studied using the standard conditions introduced above (1 eq.
C6F6, 1 eq. C6H5-Bneop, 5 mol % [Ni2(iPr2Im)4(µ-COD)], toluene as a solvent at
100 °C; Table 1, entries 14-20). All other additives, different fluorides, carbonates,
alkoxides and amines gave lower yields; the second best was provided when K3PO4
was used as the base (61 % Table 1, entry 17). The use of CsF is crucial for efficient
−
cross-coupling. The obvious advantage of F as an additive in our reactions is to avoid
the consequences of direct nucleophilic attack of the base on the perfluoroarene
substrate or polyfluoroarene containing reaction product.16 F attack is redundant
−
whereas many of the “non-fluoride” bases may react competitively with the
perfluoroarenes. Furthermore, we found that toluene is advantageous for the reaction in
comparison to THF, the use of the latter solvent gave lower yields using the standard
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conditions (Table 1, entries 1 and 21) as well as in the additive free case (Table 1,
entries 2 and 3). The reaction can be further pushed towards the product if the
fluorobenzene is used in an excess compared to the boronate ester. An increase of the
amount of C6F6 to 2 equivalents led to formation of C6H5-C6F5 3aa in 80 % yield based
on C6H5-Bneop (Table 1, entry 22).
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Table 1. Optimization of conditions for the NHC nickel-catalyzed
Suzuki-Miyaura cross-coupling reaction.a
entry
catalyst
additive
CsF
-
solvent
Toluene
Toluene
THF
yield (%) a
1
2
3
4
5
6
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9
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
-
71 b
17 b
6
-
CsF
-
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
0
iPr2Im
0
Ni(IMes)2
CsF
CsF
CsF
CsF
17
0
(iPr2Im)2NiBr2
(Me2Im)2NiI2
(iPr2Im)2Ni(CO)2
0
< 1
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(Me2Im)2Ni(CO)2
(dppe)NiCl2
CsF
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
THF
< 1
0
n-BuLi
n-BuLi
n-BuLi
KF
(dppp)NiCl2
0
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(dpppf)NiCl2
0
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
Ni2(iPr2Im)4(µ-COD)
43 b
8 b
NMe4F
KOtBu
K3PO4
K2CO3
Cs2CO3
NEt3
34 b
61 b
40 b
8 b
28 b
38 b
80 c
CsF
CsF
Toluene
a
Reaction conditions, unless otherwise stated: Ni source (10 mol % Ni), C6H5-Bneop
(0.2 mmol), C6F6 (0.2 mmol), additive (0.2 mmol), 5 mL solvent, 100 °C, 18 h. Yields
are based on C6H5-Bneop; C6H5-C6F5 was determined by GC-MS using C12H26 as
internal standard; b [Ni2(iPr2Im)4(µ-COD)] (5 mol %); c C6F6 (0.4 mmol).
To compare the reactivity of different boronate esters and the analogous boronic
acid the catalytic reaction of hexafluorobenzene and perfluorotoluene was conducted
using p-tolyl boronic acid and different p-tolyl boronate esters. The results are
presented in Table 2 and demonstrate that the neopentylglycol (p-tolyl-Bneop) and
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ethyleneglycol (p-tolyl-Beg) esters display a significantly higher reactivity than
p-tolylboronic acid, the pinacol (p-tolyl-Bpin) and catechol (p-tolyl-Bcat) ester.17
P-tolyl-Beg is the most efficient boronate ester being even more active than
p-tolyl-Bneop (Table 2, entries 2, 3, 7, 8 ). The pinacol boronate ester displays
significantly lower reactivity (Table 2, entries 4, 9). For C6F6, the reactivity trend is
p-tolyl-Beg, p-tolyl-Bneop ≫ p-tolylboronic acid, p-tolyl-Bpin > p-tolyl-Bcat, whereas
for CF3-C6F5 a slightly modified reactivity order was observed, i.e. p-tolyl-Beg,
p-tolyl-Bneop and p-tolylboronic acid reacted excellently, p-tolyl-Bpin performed less
well and p-tolyl-Bcat revealed the lowest reactivity18 (Table 2, entries 6-10).
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Table 2. NHC nickel-catalyzed Suzuki-Miyaura cross-coupling reaction: the role
of the boron component
entry
Boronic esters
p-tolyl boronic acid
p-tolyl-Beg
ArF-F
C6F6
C6F6
C6F6
C6F6
Yield (%)a
1
2
3
4
10 b
95
84
8
p-tolyl-Bneop
p-tolyl-Bpin
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p-tolyl-Bcat
C6F6
6
97 b
100
96
p-tolyl boronic acid CF3-C6F5
7
p-tolyl-Beg
p-tolyl-Bneop
p-tolyl-Bpin
p-tolyl-Bcat
CF3-C6F5
CF3-C6F5
CF3-C6F5
CF3-C6F5
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a Reaction conditions: [Ni2(iPr2Im)4(µ-COD)] (5 mol %), p-tolyl-B(OR)2 (0.2 mmol),
polyfluorinated arene (C6F6, 0.4 mmol; CF3-C6F5, 0.2 mmol), CsF (0.2 mmol), 2 mL
toluene, 100 °C, 18 h. GC yields based on boronic acid or boronate ester using C12H26
as internal standard. b K2CO3 (0.6 mmol) was employed as base.
Despite the fact that Ar-Beg is more reactive than Ar-Bneop, we chose the
neopentylglycol boronate Ar-Bneop for all subsequent experiments, as it is usually
more readily, also commercially, available for many different aryl groups.19,20 We thus
examined the use of different aryl neopentylglycol boronates for the reaction with
hexafluorobenzene. Treatment of C6F6 (2 eq.) with 4-CH3-C6H4-Bneop in toluene at
100 °C for 18 hours led to 4-CH3-C6H4-C6F5 3ab in 76 % isolated yield; C6H5-Bneop
afforded 72 % of the cross-coupling product 3aa. (Table 3, entries 1 and 2). For
4-(MeO)-C6H4-Bneop, with electron-donating methoxide substituent, the yield is
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slightly higher (82 %, Table 3, entry 2). Furthermore, 4-Ph-C6H4-Bneop reacts with
C6F6 to give 3ad in 65 % isolated yield. (Table 3, entry 4). However, for
4-F3C-C6H4-Bneop, containing the strong electron-withdrawing CF3 substituent, only
trace amounts of product were detected (Table 3, entry 5). Thus, Ar-Bneop compounds
substituted with para electron donors perform better, and those with an
electron-withdrawing substituent perform worse compared to those containing
electron-neutral substituents.
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Table 3. NHC nickel-catalyzed Suzuki-Miyaura cross-coupling reaction using
different aryl neopentylglycol boronates
Entry
Ar-Bneop
Product
Yield (%)
72
1
2a
3aa
3ab
2
76
2b
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82
65
2c
3ac
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2d
3ad
3ae
5
trace
2e
a
Isolated yields based on Ar-Bneop, unless otherwise stated. Reaction conditions:
[Ni2(iPr2Im)4(µ-COD)] (5 mol %), Ar-Bneop (2 mmol), C6F6 (4 mmol), CsF (2 mmol),
10 mL toluene, 100 °C, 18 h.
The last step of our investigations was a test of the scope of the NHC
nickel-catalyzed Suzuki-Miyaura cross-coupling reaction using different
perfluoroarenes and C6H5-Bneop (Table 4). The results reveal that octafluorotoluene,
hexafluorobenzene, perfluorobiphenyl and perfluoronaphthalene give the
corresponding products in moderate to excellent yields under our optimized conditions
(Table 4). For the reaction of C6H5-Bneop with perfluorobiphenyl and
perfluoronaphthalene, small amounts of bisborylated side products 4ca (3 %) and 4da
(4 %) were detected. For several partially fluorinated substrates such as
pentafluorobenzene, 1,2,4,5-tetrafluorobenzene and 1,3,5-trifluorobenzene, and
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p-fluortoluene only trace amounts of the cross-coupling products were detected using
the standard conditions (not shown in Table 4). However, this behavior changed when
the fluoroarene was used as the solvent. For the neat reaction of p-fluorotoluene with
C6H5-Bneop, for example, the cross-coupled product 3ea was isolated in 50 % yield
(Table 4, entry 3).
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Table 4. NHC nickel-catalyzed Suzuki-Miyaura cross-coupling reaction with
different fluoroarenes
Entry
1
ArF-F
C6F5-C6F5
1c
Procuct and Yield
3ca (61 %)b
4ca (3 %)
2
C10F8
1d
3da (48 %)c
4da (4 %)
3ea (50 %)d
3
4-H3C-C6H4F
1e
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a
b
Reported are isolated yields based on C6H5-Bneop.
Reaction conditions:
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Ni2(iPr2Im)4(µ-COD) (5 mol %), C6H5-Bneop (2 mmol), ArF-F (2 mmol), CsF (2
9
c
mmol), 10 mL toluene, 100 °C, 18 h. Reaction conditions: [Ni2(iPr2Im)4(µ-COD)] (5
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mol %), C6H5-Bneop (2 mmol), ArF-F (4 mmol), CsF (2 mmol), 10 mL toluene,
100 °C, 18 h. d 1e (2 mL), neat reaction.
In conclusion, we report that [Ni2(iPr2Im)4(µ-COD)] is an effective catalyst
precursor for the Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with
different aryl boronate esters. Among the aryl boronates used (Ar-Beg, Ar-Bneop,
Ar-Bpin and Ar-Bcat), the ethyleneglycol (aryl-Beg) and neopentylglycol (aryl-Bneop)
esters are the most efficient ones. Furthermore, the use of the additive CsF is vital to
this reaction.
EXPERIMENTAL SECTION
General Considerations. NMR spectra were recorded at ambient temperature (1H
13
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NMR, 500 MHz; C{1H}NMR, 125 MHz; F NMR, 470 MHz; F{1H}NMR, 188
1
MHz). H NMR chemical shifts are reported relative to TMS and were referenced via
residual proton resonances of the corresponding deuterated solvent (CDCl3: 7.26 ppm)
whereas 13C{1H}NMR spectra are reported relative to TMS using the carbon signals of
the deuterated solvent (CDCl3: 77.16 ppm). 19F{1H}NMR and 19F NMR spectra are
reported relative to CF3Cl. GC-MS analyses were performed using a gas
chromatograph (column: 5% phenyl methyl siloxane, 30 m, ∅ 0.25 mm, film 0.25 µm;
injector: 250 °C; oven: 40 °C (2 min), 40 °C to 280 °C (20 °C min–1); carrier gas: He
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(1.2 mL min–1)) equipped with a triple-axis MSD detector operating in EI mode and an
auto sampler/injector. High resolution mass spec were obtained with either an
atmospheric sample analysis probe (ASAP) or heated-electrospray ionization (HESI)
probe. ESI measurements were conducted using a HESI source (spray voltage 3 kV for
positive mode, capillary temperature 275 °C). ASAP measurements were conducted
using an APCI source (discharge current 3.5 kV, vaporizer temperature 300°C). Mass
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spectrometric data was acquired at
a
resolving power of 70,000
(full-width-at-half-maximum, at m/z 200, RFWHM), resulting in a scan rate of >1.5
scans/sec when using an automatic gain control target of 1.0 × 106 and a C-trap inject
time of 100 ms.
All manipulations, unless otherwise stated, were carried out under an atmosphere of
argon using conventional Schlenk, vacuum-line and glove-box techniques. All
reactions were carried out in oven-dried glassware. Toluene and THF were purified by
distillation from an appropriate drying agent (sodium with benzophenone as indicator).
Nickel catalysts, i.e., ([Ni2(iPr2Im)4(µ-COD)],9a [(iPr2Im)2Ni2Br2],12 [(Me2Im)2Ni2I2],13
[(iPr2Im)2Ni2(CO)2],14 [(Me2Im)2Ni2(CO)2],14 [(dppe)NiCl2],15 [(dppp)NiCl2]15 and
[NiIMes2]11 used were prepared according to literature procedures. Boronate esters
were prepared according to literature procedures.17 All other reagents were purchased
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from commercial suppliers, and were checked for purity by GC-MS and/or H NMR
spectroscopy and used as received.
Experimental Procedures and Characterization of Products
General Procedure for the Preparation of Products
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[Ni2(iPr2Im)4(µ-COD)] (0.1 mmol, 83 mg), CsF (2 mmol, 304 mg), Ar-Bneop (2
mmol), fluoroarene and toluene (10 mL) were added to a Schlenk tube equipped with a
magnetic stirring bar. The reaction mixture was heated at 100 °C for 18 h and after that
H2O (5 mL) was added. The product was extracted with EtOAc (3 x 50 mL) and then
the combined organic layers were dried over Na2SO4, filtered and the volatiles were
removed in vacuo. The product was purified by column chromatography on silica-gel
using hexane as the eluent. The solvent of the product containing fraction of the eluent
was evaporated in vacuo. The yields provided are based on Ar-Bneop.
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Spectroscopic Data of the Products
2,3,4,5,6-Pentafluoro-1,1'-biphenyl (3aa). Following general procedure, a white solid
in 72 % yield (351 mg) was obtained from C6F6 (4 mmol, 462 µL) and C6H5-Bneop (2
1
mmol, 380 mg). H NMR (500 MHz, CDCl3) δ = 7.52-7.45 (m, 3 H), 7.44-7.41 (m, 2
H); 13C{1H} NMR (125 MHz, CDCl3) δ = 144.2 (d of m, 1JCF = 247.3 Hz), 140.4 (d of
m, 1JCF = 253.7 Hz), 137.8 (d of m, , 1JCF = 250.9 Hz), 130.1 (t, 3JCF = 1.5 Hz), 129.3,
128.7, 126.4, 115.9 (m); 19F NMR (470 MHz, CDCl3) δ = -143.26 (m, 2 F), -155.65 (t,
J = 21.0 Hz, 1 F), -162.27 (m, 2 F); 19F{1H} NMR (188 MHz, CDCl3) δ = -143.28 (dd,
J = 8.1, 22.0 Hz, 2 F), -155.68 (t, J = 21.0 Hz, 1 F), -162.31 (td, J = 8.1, 22.0 Hz, 2 F).
HRMS (ASAP)[C12H5F5] calcd. 244.0306, found 244.0305.
Spectroscopic data for 3aa match with those previously reported in the literature.3k
2,3,4,5,6-Pentafluoro-4'-methyl-1,1'-biphenyl (3ab). Following general procedure, a
white solid in 76 % yield (390 mg) was obtained from C6F6 (4 mmol, 462 µL) and
4-CH3-C6H4-Bneop (2 mmol, 408 mg). 1H NMR (500 MHz, CDCl3) δ = 7.31 (m, 4 H),
1
2.42 (s, 3 H); 13C{1H}NMR (125 MHz, CDCl3) δ = 144.2 (d of m, JCF = 247.7 Hz),
140.2 (d of m, 1JCF = 253.3 Hz), 139.4, 137.8 (d of m, 1JCF = 250.7 Hz), 130.0, 129.5,
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123.4, 115.9 (m), 21.4; 19F NMR (470 MHz, CDCl3) δ = -143.37 (m, 2 F), -156.15 (t, J
= 18.8 Hz, 1 F), -162.46 (m, 2 F); 19F{1H} NMR (188 MHz, CDCl3) δ = -143.39 (dd, J
= 8.1, 22.8 Hz, 2 F), -156.17 (t, J = 21.0 Hz, 1 F), -162.50 (td, J = 8.1, 22.8 Hz, 2 F);
HRMS (ASAP)[C13H7F5] calcd. 258.0468, found 258.0462.
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Spectroscopic data for 3ab match with those previously reported in the literature.3k
2,3,5,6-Tetrafluoro-4'-methyl-4-(trifluoromethyl)-1,1'-biphenyl (3bb). Following
general procedure, a white solid in 90 % yield (554 mg) was obtained from
1
octafluorotoluene (2 mmol, 284 µL) and 4-CH3-C6H4-Bneop (2 mmol, 408 mg). H
NMR (500 MHz, CDCl3) δ = 7.38-7.32 (m, 4 H), 2.44 (s, 3 H); 13C{1H}NMR (125
1
1
MHz, CDCl3) δ = 144.4 (d of m, JCF = 259.5 Hz), 144.1 (d of m, JCF = 248.3 Hz),
2
140.3, 129.8 (t, 3JCF = 2.1 Hz), 129.6, 125.0 (t, JCF = 16.4 Hz), 123.1, 120.9 (d of m,
3
1JCF = 274.0 Hz), 108.2 (m), 21.4; 19F NMR (470 MHz, CDCl3) δ = -56.20 (t, JFF =
18.8 Hz, 3 F), -140.98 (m, 2 F), -141.70 (m, 2 F); 19F{1H} NMR (188 MHz, CDCl3) δ
3
= -56.24 (t, JFF = 21.4 Hz, 3 F), -141.03 (m, 2 F), -141.75 (m, 2 F). HRMS
(ASAP)[C14H7F7] calcd. 308.0430, found 308.0422.
Spectroscopic data for 3bb match with those previously reported in the literature.3k
2,3,4,5,6-Pentafluoro-4'-methoxy-1,1'-biphenyl (3ac). Following general procedure,
a white solid in 82 % yield (449 mg) was obtained from C6F6 (4 mmol, 462 µL) and
p-OMe-C6H4-Bneop (2 mmol, 440 mg). 1H NMR (500 MHz, CDCl3) δ = 7.37-7.35 (m,
2 H), 7.03-7.01 (m, 2 H), 3.87 (s, 3 H); 13C{1H}NMR (125 MHz, CDCl3) δ = 160.3,
144.2 (d of m, 1JCF = 247.0 Hz), 140.0 (d of m, 1JCF = 253.3 Hz), 137.8 (d of m, 1JCF
=
250.5 Hz), 131.4 (t, 3JCF = 1.8 Hz), 118.4, 115.7 (m), 114.2, 55.4; 19F NMR (470 MHz,
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CDCl3) δ = -143.62 (dd, J = 8.1, 22.0 Hz, 2 F), -156.51 (t, J = 21.1 Hz, 1 F), -162.54
(td, J = 8.1, 21.8 Hz, 2 F); 19F{1H} NMR (188 MHz, CDCl3) δ = = -143.66 (dd, J = 8.0,
22.8 Hz, 2 F), -156.56 (t, J = 22.0 Hz, 1 F), -162.59 (td, J = 8.0, 22.0 Hz, 2 F). HRMS
(ASAP)[C13H7F5O] calcd. 274.0412, found 274.0409.
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Spectroscopic data for 3ac match with those previously reported in the literature.5l
2,3,4,5,6-Pentafluoro-1,1':4',1''-terphenyl (3ad). Following general procedure, a
white solid in 65 % yield (416 mg) was obtained from C6F6 (4 mmol, 462 µL) and
1
PhBneop (2 mmol, 532 mg). H NMR (500 MHz, CDCl3) δ = 7.73-7.66 (m, 2 H),
7.65-7.63 (m, 2 H), 7.52-7.46 (m, 4 H), 7.41-7.38 (tt, J = 1.3, 7.4 Hz, 1 H);
13C{1H}NMR (125 MHz, CDCl3) δ = 142.2, 140.2, 130.6, 128.9, 127.8 127.4, 127.2;
due to the low solubility of the compound in CDCl3 the C-F resonances have not been
detected. 19F NMR (470 MHz, CDCl3) δ = -143.13 (m, 2 F), -155.50 (t, J = 20.9 Hz, 1
19
F), -162.12 (m, 2 F); F{1H} NMR (188 MHz, CDCl3) δ = -143.15 (dd, J = 8.1, 22.8
Hz, 2 F), -155.54 (t, J = 21.0 Hz, 1 F), -162.12 (td, J = 8.1, 22.8 Hz, 2 F). HRMS
(ASAP) [C18H10F5]+ (M+H)+ calcd. 321.0697, found 321.0691.
Spectroscopic data for 3ad match with those previously reported in the literature.21
2,2',3,3',4,5,5',6,6'-Nonafluoro-1,1':4',1''-terphenyl (3ca). Following general
procedure, a white solid in 61 % yield (478 mg) was obtained from perfluorodiphenyl
(2 mmol, 668 mg) and C6H5-Bneop (2 mmol, 380 mg). 1H NMR (500 MHz, CDCl3) δ
= 7.56-7.49 (m, 5 H); 13C{1H}NMR (125 MHz, CDCl3) δ = 144.1 (d of m, 1JCF = 253.1
Hz), 144.4 (d of m, 1JCF = 252.6 Hz), 144.0 (d of m, 1JCF = 248.3 Hz), 141.0 (m), 137.9
1
3
3
(d of m, JCF = 253.7 Hz), 130.1 (t, JCF = 2.0 Hz), 129.6, 128.8, 126.8 (t, JCF = 2.1
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Hz), 123.0 (t, JCF = 16.5 Hz), 103.7 (d of m, 1JCF = 301.0 Hz), 100.0; 19F NMR (470
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MHz, CDCl3) δ = -137.28 (m, 2 F), -138.68 (m, 2 F), -142.54 (m, 2 F), -150.37 (m, 1
9
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F), -160.58(m, 2 F); F{1H} NMR (188 MHz, CDCl3) δ = -137.28 (m, 2 F), -138.68
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(m, 2 F), -142.54 (m, 2 F), -150.37 (tt, JFF = 2.7, 21.0 Hz, 1 F), -160.58 (m, 2 F).
HRMS (ASAP)[C18H5F9] calcd. 392.0247, found 392.0235. Spectroscopic data for 3ca
match with those previously reported in the literature.9b
2',2'',3',3'',5',5'',6',6''-Octafluoro-1,1':4',1'':4'',1'''-quaterphenyl (4ca). 4ca (25 mg,
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3 %) was obtained as a side product from the reaction mixture of 3ca. H NMR (500
13
MHz, CDCl3) δ = 7.55-7.49 (m, 10 H, aryl-H); C{1H}NMR (125 MHz, CDCl3) δ =
3
130.1 (t, JCF = 1.8 Hz), 129.6, 128.7; due to the low solubility of the compound in
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CDCl3 the C-F resonances have not been detected. F NMR (470 MHz, CDCl3) δ =
-138.58 (m, 4 F), -142.85 (m, 4 F); 19F{1H} NMR (188 MHz, CDCl3) δ = -138.60 (m,
4 F), -142.88 (m, 4 F). HRMS (ASAP)[C24H10F8H]＋(M＋H)＋ calcd. 451.0728, found
451.0711.
Spectroscopic data for 4ca match with those previously reported in the literature.22
1,2,3,4,5,6,8-Heptafluoro-7-phenylnaphthalene (3da). Following general procedure,
a white solid in 48 % yield (316 mg) was obtained from perfluoronaphthalene (4 mmol,
1
1088 mg) and C6H5-Bneop (2 mmol, 380 mg). H NMR (500 MHz, CDCl3) δ =
3
7.55-7.49 (m, 5 H); 13C{1H}NMR (125 MHz, CDCl3) δ = 130.3 (t, JCF = 1.9 Hz),
129.4, 128.7, 127.1 (d, JCF = 1.9 Hz) due to the low solubility of the compound in
CDCl3 the C-F resonances have not been detected; 19F NMR (470 MHz, CDCl3) δ =
-121.49 (ddd, J = 4.0, 19.8, 74.6 Hz, 1 F), -136.90 (m, 1 F), -143.73 (m, 1 F), -146.18
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(m, 1 F), -148.72 (m, 1 F), -153.52 (td, J = 2.7, 18.5 Hz, 1 F), -155.64 (m, 1 F); 19F{1H}
NMR (188 MHz, CDCl3) δ = -121.50 (ddd, J = 3.8, 18.6, 70.4 Hz, 1 F), -136.92 (m, 1
F), -143.76 (dtt, J = 3.4, 16.9, 70.4 Hz, 1 F), -146.19 (m, 1 F), -148.76 (dtt, J = 4.1,
18.2, 57.3 Hz, 1 F), -153.56 (tt, J = 3.4, 18.6 Hz, 1 F), -155.67 (m, 1 F). HRMS
(ASAP)[C16H5F7] calcd. 330.0274, found 330.0269.
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Spectroscopic data for 3da match with those previously reported in the literature.23
1,2,4,5,6,8-hexafluoro-3,7-diphenylnaphthalene (4da). 4da (30 mg, 4 %) was
1
obtained as a side product from the reaction mixture of 3da. H NMR (500 MHz,
13
CDCl3) δ = 7.57-7.48 (m, 10 H, aryl-H); C{1H}NMR (125 MHz, CDCl3) δ = 130.4,
3
129.3, 128.6, 127.5 (d, JCF = 2.0 Hz); due to the low solubility of the compound in
19
CDCl3 the C-F resonances have not been detected. F NMR (470 MHz, CDCl3) δ =
-122.65 (m, 2 F), -138.94 (m, 2 F), -147.50 (m, 2 F); 19F{1H} NMR (188 MHz, CDCl3)
δ = -122.65 (m, 2 F), -138.95 (m, 2 F), -147.51 (m, 2 F). HRMS (ASAP)[C22H10F6H]＋
(M＋H)＋ calcd. 389.0759, found 389.0752. Elemental analysis for C22H10F6 (388.30
[g/mol]): C, 67.78 (68.05); H, 2.58 (2.60). Melting point (uncorrected): 203-205 °C.
4-methyl-1,1'-biphenyl (3ea). Following the general procedure, a white solid in 50 %
yield (168 mg) was obtained from the reaction of p-fluorotoluene (2 mL) and
1
C6H5-Bneop (2 mmol, 380 mg) without toluene as the solvent. H NMR (500 MHz,
CDCl3) δ = 7.60-7.58 (m, 2 H), 7.52-7.50 (m, 2 H), 7.45-7.42 (m, 2 H), 7.35-7.32 (m, 1
H), 7.27-7.26 (m, 2 H), 2.41 (s, 3 H); 13 C{1H} NMR (125 MHz, CDCl3; ) δ = 141.2,
138.4, 137.0, 129.5, 128.7, 127.02, 127.0, 126.99, 21.1. HRMS (ASAP) [C13H13]+
(M+H)+ calcd. 169.1012, found 169.1006.
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Spectroscopic data for 3ea match with those previously reported in the literature..24
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AUTHOR INFORMATION
Corresponding Authors
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*E-mail: u.radius@uni-wuerzburg.de
*E-mail: todd.marder@uni-wuerzburg.de
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENT
This work was supported by the University of Würzburg and the Deutsche
Forschungsgemeinschaft DFG (Ra720/12-1). J.Z. thanks the China Scholarship
Council for supporting her stay in Würzburg.
Supporting information
The Supporting Information is available free of charge on the ACS Publications
website. Copies of 1H, 13C{1H}, 19F NMR and 19F{1H}NMR spectra, and GC-MS data
(PDF). Crystal data for 4da. (CIF)
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