Palladium-Catalyzed Cross-Coupling of Furfuryl Alcohols with Arylboronic Acids via Aromatization-Driven Carbon?Carbon Bond Cleavage to Synthesize 5-Arylfurfuryl Alcohols and 2,5-Diaryl Furans

Article abstract of DOI:10.1002/adsc.201900799

Herein we report a protocol for novel palladium-catalyzed cross-coupling reactions of sustainably produced primary furfuryl alcohols with arylboronic acids to deliver 5-arylfurfuryl alcohols and 2,5-diaryl furans. Hammett plot analysis suggested that the reaction mechanism involved aromatization-driven cleavage of the carbon?carbon bond of a furan oxonium ion intermediate. This protocol provides a simple, practical way to transform 5-hydroxymethylfurfural into useful compounds. (Figure presented.).

Full text of DOI:10.1002/adsc.201900799

Title: Palladium-Catalyzed Cross-Coupling of Furfuryl Alcohols with
Arylboronic Acids via Aromatization-Driven Carbon–Carbon Bond
Cleavage to Synthesize 5-Arylfurfuryl Alcohols and 2,5-Diaryl
Furans
Authors: Biaolin Yin and Guanghao Huang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900799
Link to VoR: http://dx.doi.org/10.1002/adsc.201900799

10.1002/adsc.201900799
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-Catalyzed Cross-Coupling of Furfuryl Alcohols with
Arylboronic Acids via Aromatization-Driven Carbon–Carbon
Bond Cleavage to Synthesize 5-Arylfurfuryl Alcohols and 2,5-
Diaryl Furans
Guanghao Huanga and Biaolin Yina*
a
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical
Engineering, South China University of Technology, Guangzhou 510640, P. R. of China
E-mail: blyin@scut.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Herein we report a protocol for novel palladium-
catalyzed cross-coupling reactions of sustainably produced
primary furfuryl alcohols with arylboronic acids to deliver 5-
arylfurfuryl alcohols and 2,5-diaryl furans. Hammett plot
analysis suggested that the reaction mechanism involved
aromatization-driven cleavage of the carbon–carbon bond of
a furan oxonium ion intermediate. This protocol provides a
simple, practical way to transform 5-hydroxymethylfurfural
into useful compounds.
Keywords: C–C activation; Cleavage reactions; Cross-
coupling; Primary alcohols; Synthetic methods
examples of C–C bond cleavage reactions of primary
alcohols, albeit with low yields.[6b,c] In addition,
aromatization has proved to be a driving force for C–
C bond cleavage, but only a few examples have been
reported.[7] Therefore, development of novel C–C
Introduction
Carbon–carbon bond cleavage reactions have
attracted considerable attention owing to their utility
in the synthesis of valuable chemicals.[1] For example, bond cleavage reactions that take advantage of
C–C bonds cleavage has been used to produce
biomass-based fuels.[2] Attempts have been made to
use homogeneous transition-metal complexes to
catalyze C–C bond cleavage, but this process is
challenging because of the high thermodynamic
stability of such bonds.[3] One widely used strategy
for cleaving C–C bonds is to take advantage of ring
strain; that is, the energy required for dissociation of
a C–C bond can be compensated for by the release of
ring strain energy.[4] However, for unstrained
molecules, some other driving force, such as the
departure of a good leaving group or the presence of
a chelation auxiliary to lower the energy of a reaction
intermediate, is required for C–C bond cleavage. For
example, ketones have been used as leaving groups in
β-C cleavage reactions of tertiary alcohols,[5] and N-
containing directing groups have been successfully
used to accomplish C–C bond cleavage reactions of
secondary alcohols.[6] In contrast, there have been
only a few examples of direct catalytic C–C bond
cleavage reactions of primary alcohols, because
oxidation of the hydroxyl groups of such compounds
to aldehydes occurs more readily than C–C bond
cleavage. However, Shi and co-workers reported two
aromatization would be highly desirable.
Arylfurans, including 2-arylfurans and 2,5-diaryl
furans, which have interesting bioactivities[8] and
physical properties,[9] are usually synthesized by
construction of the furan ring from alkynes[10] or by
cross-coupling
reactions
of
environmentally
unfriendly halides or organotin reagents.[11] Recently,
Forgione and co-workers described palladium-
catalyzed decarboxylative cross-coupling reactions of
sustainably sourced 2,5-furandicarboxylic acid with
aryl halides to access symmetric 2,5-diaryl furans,
although the reaction conditions were harsh.[12] Very
recently, we reported a method for synthesizing 2,5-
diaryl furans by means of oxidative C–C bond
cleavage reactions of primary alcohols (5-aryl
furfuryl alcohols) driven by aromatization of a furan
oxonium ion intermediate (Scheme 1).[13] However,
the necessary 5-aryl furfuryl alcohol starting
materials were obtained mainly by Suzuki coupling
reactions, which lack atom- and step-economy and
involve unreadily available starting materials. We
envisioned that 5-aryl furfuryl alcohols 2 could be
synthesized from 2,5-furandimethanol derivatives 1
by selective C–C bond cleavage and then used to
1
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10.1002/adsc.201900799
Advanced Synthesis & Catalysis
construct 2,5-diaryl furans 3. 2,5-Furandimethanol
derivatives 1 can be prepared easily from 5-
hydroxymethylfurfural (HMF), which is produced on
a large scale by hydrolysis of fructose.
found to offer no improvement in the yield (entries
15–20). Increasing the Pd(PhCN)2Cl2 loading to 10
mol % also failed to improve the yield (entry 21).
Gratifyingly, prolonging the reaction time to 20 h
increased the yield to 61% (entry 22). When the
K2CO3 additive was replaced with Na2CO3, Cs2CO3,
KHCO3, KOAc, or KOH, the yield dropped markedly
(see SI for details). Moreover, control experiments
revealed that the reaction did not proceed in the
absence of the palladium catalyst, ligand, or additive
(entries 23–25). On the basis of the above-described
results, we concluded that the optimal conditions for
this reaction involved the use of Pd(PhCN)2Cl2 (5
mol %) as the catalyst, L1 (10 mol %) as the ligand,
K2CO3 (100 mol %) as the additive, PhF as the
solvent, and 60 °C as the reaction temperature (entry
22).
Table 1. Optimization of reaction conditions.a)
Scheme 1. Transition-metal-catalyzed C–C bond cleavage
reactions of furfuryl alcohols.
Ent
ry
Yield
(%)b)
1
[Pd]
Ligand
2
1
2
3
4
5
6
7
8
1a
1b
1c
1d
1e
1f
1g
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
Pd(OAc)2
PdBr2
PdCl2
Pd(TFA)2
Pd(dppf)Cl2
Pd(CH3CN)2Cl2
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
—
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L5
L6
L7
L8
L1
L1
L1
L1
L1
L1
L1
L1
L1
—
L1
2aa trace
2ba 55
2ca 35
2da 40
2ea 38
2fa trace
2ga trace
2ba trace
2ba 23
2ba 27
2ba trace
2ba 28
2ba 27
2ba 25
2ba 24
2ba 31
2ba 17
2ba trace
Results and Discussion
We began by evaluating conditions for reactions of
2,5-furandimethanol derivatives 1 with phenylboronic
acid as a model system (Table 1). When 1a (R = H,
100 mol %) and phenylboronic acid (350 mol %)
were exposed to O2 as the terminal oxidant in the
presence of a catalyst assembled in situ from
Pd(PhCN)2Cl2 (5 mol %) and 1,10-phenanthroline
(10 mol %) in PhF (1.5 mL) containing K2CO3 (100
mol %) at 60 °C, only a trace of desired product 2aa
was observed, along with a highly complicated
mixture of various by-products, including HMF and
furan-2,5-dicarbaldehyde (entry 1). To suppress the
side reactions, we introduced a series of mono-
protecting groups (R) on 1a. To our delight, when a
substrate with a TBS ether protecting group (1b) was
used, the reaction smoothly afforded desired product
2ba in 55% isolated yield (entry 2). Increasing the
size of the protecting group (R = TBDPS) decreased
the yield (2ca, entry 3), as did the use of a smaller
protecting group, such as Me or Bn (entries 4 and 5).
When R was a good leaving group (Ac or Bz), a
complex mixture containing only a trace of the 5-
arylfurfuryl alcohol product (2fa or 2ga, respectively)
was detected (entries 6 and 7).
9
10
11
12
13
14
15
16
17
18
19
20
2ba
8
2ba 28
2ba 55
2ba 61
2ba ND
2ba ND
2ba trace
21c) 1b
22d) 1b
23
24
1b
1b
Pd(PhCN)2Cl2
Pd(PhCN)2Cl2
25e) 1b
Next, we surveyed a number of bidentate nitrogen
ligands in reactions of 1b (Table 1, entries 8–14). 2,9-
Dimethyl-1,10-phenanthroline (L2) and 1,10-
phenanthroline-5,6-dione (L5) gave only traces of
2ba, demonstrating that sterically hindered or
electron-deficient ligands negatively affected the
reaction (entries 8 and 11). Several commercially
available palladium catalysts were screened and
a)
Reaction conditions, unless otherwise noted: 1 (0.25
mmol), PhB(OH)2 (350 mol %), Pd catalyst (5 mol %),
ligand (10 mol %), additive (100 mol %), O2 (in a balloon),
2
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10.1002/adsc.201900799
Advanced Synthesis & Catalysis
PhF (1.5 mL), 60 °C, 15 h. b) Isolated yields are given. ND
acid gave only a trace of 2bn, indicating that this
reaction was sensitive to the steric bulk of the
arylboronic acid. 3,5-Disubstituted phenylboronic
acids were well tolerated, affording coupling products
2bo and 2bp in good yields. 3,4-Disubstituted and
3,4,5-trisubstituted phenylboronic acids produced the
corresponding products (2bq–2bs), albeit in
relatively low yields. In contrast, phenylboronic acids
with an electron-withdrawing group (F, Cl, Br, CF3,
Ph, COOEt, or NO2) at the para-position gave poor
yields of coupling products 2bt–2bz. Finally,
evaluation of naphthylboronic acids confirmed the
negative effect of steric bulk on this transformation.
Specifically, the coupling of 1b with 2-
naphthylboronic acid provided 2baa in moderate
yield, whereas more hindered 1-naphthylboronic acid,
gave only a trace of desired product 2bab.
c)
d)
= not detected.
Reaction was carried out for 20 h. Reaction was carried
out without K2CO3.
10 mol % Pd catalyst was used.
e)
With the optimized conditions in hand, we
evaluated the scope of the transformation of TBS-
protected substrate 1b with a wide array of
arylboronic acids (Table 2). Coupling of 1b with
phenylboronic acids bearing an electron-donating
group at the para- or meta-position gave the
corresponding products (2bb–2bm) in 42–61%
isolated yields. Notably, commensurate yields were
obtained when the scale of the reaction was increased
from 0.5 to 5 mmol (2ba: 59% vs 56%; 2bi: 61% vs
58%). An ortho-methyl-substituted phenylboronic
Table 2. Oxidative coupling reactions of primary alcohol 1b with various arylboronic acids.a)
a)
Reaction conditions: 1b (0.5 mmol), ArB(OH)2 (350 mol %), Pd(PhCN)2Cl2 (5 mol %), L1 (10 mol %), K2CO3 (100
b)
mol %), O2 (in a balloon), PhF (3.0 mL), 60 °C, 20 h. Isolated yields are provided. ND = not detected. Reaction
performed on a 5 mmol scale. Isolated yields (over two steps from 1b) of the corresponding alcohol after deprotection
c)
are provided.
In addition to the primary alcohol, secondary and
tertiary alcohols were explored to determine their
suitability for this transformation (Table 3).
Secondary alcohols underwent coupling reactions
with m-tolylboronic acid to give 2bi in low yields,
and increasing the steric hindrance around the
hydroxyl group decreased the yield sharply (1h > 1i >
1j > 1k). Tertiary alcohols (1l and 1m) showed even
lower reactivities under these conditions.
Entry
1
R1
H
R2
H
H
H
H
H
Me
Ph
2bi (yield [%])b)
61
29
21
trace
ND
trace
ND
1
2
3
4
5
6
1b
1h
1i
1j
1k
1l
Me
Et
iPr
tBu
Me
Ph
7
1m
a)
Table 3. Oxidative coupling reactions of furfuryl alcohols
1 with m-tolylboronic acid.a)
Reaction conditions: 1 (0.50 mmol), m-TolB(OH)2 (350
mol %), Pd(PhCN)2Cl2 (5 mol %), L1 (10 mol %), K2CO3
3
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10.1002/adsc.201900799
Advanced Synthesis & Catalysis
(100 mol %), O2 (in a balloon), PhF (3.0 mL), 60 °C, 20 h.
b) Isolated yields are given. ND = not detected.
On the basis of our previous research on furan
chemistry[14] and the known mechanism of palladium-
catalyzed β-C elimination reactions of tertiary[5] and
secondary alcohols[6], we propose two possible
pathways for the C–C bond cleavage reactions
reported herein (Scheme 2): (a) aromatization-driven
cleavage of the C–C bond of a furan oxonium ion
intermediate and (b) a direct β-C elimination reaction
of an alcoholate. To evaluate the likelihood of these
two possibilities, we performed a Hammett plot
analysis (Scheme 3). When furfuryl alcohols bearing
various substituted phenyl groups were employed as
substrates under the optimal conditions, Hammett
plot analysis clearly revealed that the rate of this
transformation increased as the electron density of the
C5-substituent of the furfuryl alcohol increased. The
negative slope (ρ = −0.56) of the Hammett plot
indicated the existence of a charged transition state,
which is consistent with a furan oxonium ion
intermediate (path a). In addition, arylation of
sterically bulky secondary and tertiary alcohol
substrates is disfavored, which is incompatible with
the involvement of path b.
Because a number of compounds with 2,5-diaryl
furan moieties have remarkable bioactivities and high
luminescence efficiencies,[8,9] we explored the use of
the above-described C–C bond cleavage reaction for
the synthesis of 2,5-diaryl furans 3 from (5-(m-
tolyl)furan-2-yl)methanol 2bi, which was obtained
by deprotection of 2bi (see SI for details). As shown
in Table 4, the results of coupling reactions between
primary furfuryl alcohol 2bi and arylboronic acids
were similar to those shown in Table 2. That is,
electron-rich phenylboronic acids with an alkyl or
alkoxy group at the meta- or para-position delivered
the corresponding products (3b–3f) in good isolated
yields (Table 4, entries 2–6). In contrast, a sterically
hindered ortho-methyl-substituted phenylboronic acid
afforded 3g in a low yield (entry 7). Coupling of 2bi
with 3,5-dimethyl and 3,5-dimethoxyl phenylboronic
acid proceeded smoothly to produce good yields of
3h and 3i, respectively (entries 8 and 9). Among the
electron-deficient arylboronic acids that we tested,
halogenated arylboronic acids were well tolerated,
giving 3j–3l in good yields (entries 10–12); however,
extremely electron-deficient arylboronic acids
afforded only very low yields of the corresponding
products (3m–3o, entries 13–15). Finally, although 1-
naphthylboronic acid gave only a 12% yield of
desired product 3p, the less sterically bulky 2-
naphthylboronic acid provided 3q in 55% yield
(entries 16 and 17).
Table 4. Oxidative coupling reactions of 2bi with various
arylboronic acids.a)
Scheme 2. Two possible pathways for cleavage of the C–C
bonds of furfuryl alcohols.
Entry
1
2
3
4
Ar
Ph
3
Yield (%)b)
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3n
3o
3p
3q
74
69
65
68
62
60
23
66
58
61
52
45
17
17
Trace
12
55
3-MeC6H4
4-MeC6H4
3-MeOC6H4
4-MeOC6H4
4-tBuC6H4
2-MeC6H4
3,5-diMeC6H3
3,5-diMeOC6H3
4-FC6H4
5
6c)
7
8
9
10
11
12
13
14
15
16
4-BrC6H4
4-ClC6H4
4-COOEtC6H4
4-CF3C6H4
4-NO2C6H4
1-Naphthyl
2-Naphthyl
17
a)
Reaction conditions, unless otherwise noted: 2bi (0.5
mmol), ArB(OH)2 (1.25 mmol), Pd(OAc)2 (5 mol %), L7
(12 mol %), KF (200 mol %), O2 (in a balloon), DCE (1.5
b)
c)
mL), 70 °C, 15 h. Isolated yields are given. Reaction
was carried out in 2.5 mL of DCE.
Scheme 3. Hammett plot for cleavage of the C–C bond of
furfuryl alcohols.
4
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10.1002/adsc.201900799
Advanced Synthesis & Catalysis
26.1, 18.6, -5.0. IR (film) 3062, 2955, 2931, 2858, 1549,
1468, 1255, 1078, 838, 780 cm-1. HRMS (ESI) m/z calcd
for C17H24NaO2Si [M+Na]+: 311.1443, found: 311.1440.
Conclusion
In summary, we have expanded the scope of the
palladium-catalyzed oxidative coupling reaction
between commercially available arylboronic acids
and primary furfuryl alcohols for sustainable
synthesis of 5-arylfurfuryl alcohols and 2,5-diaryl
furans. The primary furfuryl alcohol substrates can be
prepared readily from 5-hydroxymethylfurfural.
Hammett plot analysis demonstrated that the C–C
bond cleavage involved in this transformation was
driven by aromatization of a furan oxonium ion
intermediate. Taken together, our results indicate that
this novel protocol offers a simple, practical route for
transformation of sustainably produced 5-
hydroxymethylfurfural into useful compounds.
tert-Butyldimethyl((5-(p-tolyl)furan-2-
yl)methoxy)silane (2bb)
1
Yellow oil (81.0 mg, 54%). H NMR (400 MHz, CDCl3) δ
7.58 (d, J = 7.7 Hz, 2H), 7.20 (d, J = 7.7 Hz, 2H), 6.54 (s,
1H), 6.31 (s, 1H), 4.72 (s, 2H), 2.37 (s, 3H), 0.95 (s, 9H),
0.15 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 153.8, 153.7,
137.1, 129.4, 128.4, 123.8, 109.5, 105.0, 58.5, 26.1, 21.4,
18.6, -5.0. IR (film) 3027, 2954, 2930, 2858, 1553, 1498,
1254, 1078, 838, 780 cm-1. HRMS (ESI) m/z calcd for
C18H26KO2Si [M+K]+: 341.1339, found: 341.1337.
tert-Butyl((5-(4-ethylphenyl)furan-2-
yl)methoxy)dimethylsilane (2bc)
1
Yellow oil (79.0 mg, 50%). H NMR (400 MHz, CDCl3) δ
7.61 (d, J = 7.9 Hz, 2H), 7.23 (d, J = 7.9 Hz, 2H), 6.55 (d,
J = 3.1 Hz, 1H), 6.32 (d, J = 3.1 Hz, 1H), 4.72 (s, 2H),
2.68 (q, J = 7.5 Hz, 2H), 1.27 (t, J = 7.5 Hz, 3H), 0.96 (s,
9H), 0.15 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 153.9,
153.7, 143.6, 128.7, 128.3, 123.9, 109.5, 105.1, 58.5, 28.8,
26.1, 18.6, 15.6, -5.0. IR (film) 3028, 2959, 2931, 2858,
1551, 1498, 1254, 1078, 836, 779 cm-1. HRMS (ESI) m/z
calcd for C19H28KO2Si [M+K]+: 355.1496, found:
355.1493.
Experimental Section
General procedure for the synthesis of arylfurans 2
1 (0.5 mmol) was added to a 25-mL dried Schlenk tube
charged with arylboronic acids (1.75 mmol),
Pd(PhCN)2Cl2 (5 mol %, 9.6 mg), 1,10-phenanthroline (L1,
10 mol %, 10.0 mg), K2CO3 (0.5 mmol, 70.0 mg), and
fluorobenzene (3.0 mL). The mixture was stirred at 60 °C
for 20 h under O2 atmosphere (in a balloon), and then was
cooled to room temperature. The resultant mixture was
evaporated in vacuum and further isolated by flash
chromatography on silica gel with petroleum ether to give
the pure product 2.
tert-Butyldimethyl((5-(4-propylphenyl)furan-2-
yl)methoxy)silane (2bd)
1
Yellow oil (76.0 mg, 46%). H NMR (400 MHz, CDCl3) δ
7.59 (d, J = 7.9 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 6.54 (d,
J = 3.1 Hz, 1H), 6.31 (d, J = 3.1 Hz, 1H), 4.71 (s, 2H),
2.61 (t, J = 7.6 Hz, 2H), 1.72 – 1.61 (m, 2H), 0.99 – 0.93
(m, 12H), 0.14 (s, 6H). 13C NMR (100 MHz, CDCl3) δ
153.9, 153.7, 142.0, 128.9, 128.7, 123.8, 109.5, 105.1, 58.5,
38.0, 26.1, 24.6, 18.6, 13.9, -5.0. IR (film) 3026, 2957,
2930, 2858, 1498, 1465, 1255, 1078, 838, 780 cm-1.
HRMS (ESI) m/z calcd for C20H30KO2Si [M+K]+:
369.1652, found: 369.1648.
General procedure for the synthesis of 5-aryl furfuryl
alcohols 2’
Before being isolated by flash chromatography, the
resultant mixture of 2 was dissolved in THF (5 mL), then
tetrabutylammonium fluoride (1 M solution in THF, 150
mol % based on 1b) was added. After being stirred for 1 h,
H2O (15 mL) was added and the mixture was concentrated
in vacuo to remove the THF. The remaining aqueous
mixture was extracted with EtOAc (3 × 10 mL). The
combined organic layers were dried over Na2SO4 and
concentrated in vacuo, and then was purified by silica gel
chromatography (petroleum ether/EtOAc = 20:1) to give
the corresponding alcohol 2’.
tert-Butyl((5-(4-isopropylphenyl)furan-2-
yl)methoxy)dimethylsilane (2be)
1
Yellow oil (69.3 mg, 42%). H NMR (400 MHz, CDCl3) δ
7.46 (d, J = 7.9 Hz, 2H), 7.11 (d, J = 7.9 Hz, 2H), 6.39 (d,
J = 2.1 Hz, 1H), 6.16 (d, J = 2.1 Hz, 1H), 4.57 (s, 2H),
2.84 – 2.69 (m, 1H), 1.14 (d, J = 6.9 Hz, 6H), 0.81 (s, 9H),
-0.00 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 153.9, 153.7,
148.2, 128.8, 126.8, 123.9, 109.5, 105.1, 58.5, 34.0, 26.1,
24.0, 18.6, -5.0. IR (film) 3026, 2958, 2931, 2859, 1498,
1465, 1255, 1075, 836, 780 cm-1. HRMS (ESI) m/z calcd
for C20H30KO2Si [M+K]+: 369.1652, found: 369.1646.
General procedure for the synthesis of 2,5-diaryl furans
3
2bi’ (0.5 mmol) was added to an 25-mL dried Schlenk tube
charged with arylboronic acids (1.25 mmol), Pd(OAc)2 (5
mol %, 5.6 mg), L7 (12 mol %, 11.0 mg), KF (1.0 mmol,
58.0 mg), and 1,2-dichloroethane (1.5 mL). The mixture
was stirred at 70 °C for 15 h under O2 atmosphere (in a
balloon), and then was cooled down to room temperature.
The resultant mixture was evaporated in vacuum and
further isolated by flash chromatography on silica gel with
petroleum ether to give the pure product 3.
tert-Butyl((5-(4-(tert-butyl)phenyl)furan-2-
yl)methoxy)dimethylsilane (2bf)
1
Yellow oil (74.0 mg, 43%). H NMR (400 MHz, CDCl3) δ
7.63 (d, J = 7.2 Hz, 2H), 7.43 (d, J = 7.2 Hz, 2H), 6.56 (s,
1H), 6.33 (s, 1H), 4.73 (s, 2H), 1.37 (s, 9H), 0.97 (s, 9H),
0.16 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 153.8, 153.7,
150.4, 128.4, 125.7, 123.6, 109.5, 105.2, 58.5, 34.7, 31.4,
26.1, 18.6, -5.0. IR (film) 3027, 2958, 2931, 2859, 1553,
1495, 1256, 1080, 837, 781 cm-1. HRMS (ESI) m/z calcd
for C21H32KO2Si [M+K]+: 383.1809, found: 383.1805.
Characterizing data for previously unreported
molecules
tert-Butyldimethyl((5-phenylfuran-2-yl)methoxy)silane
(2ba)
(5-(4-Methoxyphenyl)furan-2-yl)methanol (2bg’)[15]
1
1
White solid (46.0 mg, 45% over two steps from 1b). H
Yellow oil (85.0 mg, 59%). H NMR (400 MHz, CDCl3) δ
NMR (400 MHz, CDCl3) δ 7.59 (d, J = 8.8 Hz, 2H), 6.91
(d, J = 8.8 Hz, 2H), 6.45 (d, J = 3.2 Hz, 1H), 6.34 (d, J =
3.2 Hz, 1H), 4.63 (s, 2H), 3.82 (s, 3H), 2.11 (br, 1H). 13C
7.53 (d, J = 7.7 Hz, 2H), 7.23 (t, J = 7.5 Hz, 2H), 7.11 (t, J
= 7.2 Hz, 1H), 6.45 (s, 1H), 6.18 (s, 1H), 4.57 (s, 2H), 0.81
(s, 9H), -0.00 (s, 6H). 13C NMR (100 MHz, CDCl3) δ
154.1, 153.6, 131.1, 128.8, 127.3, 123.8, 109.6, 105.8, 58.5,
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900799
Advanced Synthesis & Catalysis
NMR (100 MHz, CDCl3) δ 159.2, 154.2, 153.0, 125.4,
1H), 5.14 (s, 2H), 4.73 (s, 2H), 0.97 (s, 9H), 0.16 (s, 6H).
13C NMR (100 MHz, CDCl3) δ 159.2, 154.1, 153.3, 137.1,
132.4, 129.9, 128.7, 128.1, 127.7, 116.7, 114.0, 110.2,
109.6, 106.2, 70.2, 58.5, 26.1, 18.6, -5.0. IR (film) 3028,
2954, 2929, 2857, 1539, 1453, 1257, 1071, 837, 776 cm-1.
HRMS (ESI) m/z calcd for C24H30KO3Si [M+K]+:
433.1601, found: 433.1598.
123.9, 114.2, 110.1, 104.2, 57.7, 55.4.
((5-(4-(Benzyloxy)phenyl)furan-2-yl)methoxy)(tert-
butyl)dimethylsilane (2bh)
o
1
White solid (82.8 mg, 42%), mp: 57-58 C. H NMR (400
MHz, CDCl3) δ 7.62 (d, J = 7.7 Hz, 2H), 7.49 – 7.33 (m,
5H), 7.02 (d, J = 7.7 Hz, 2H), 6.48 (s, 1H), 6.32 (s, 1H),
5.11 (s, 2H), 4.72 (s, 2H), 0.97 (s, 9H), 0.16 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ 158.3, 153.6, 153.4, 137.0,
tert-Butyl((5-(3,5-dimethylphenyl)furan-2-
yl)methoxy)dimethylsilane (2bo)
1
128.7, 128.1, 127.6, 125.2, 124.4, 115.2, 109.5, 104.2, 70.2, Yellow oil (82.8 mg, 53%). H NMR (400 MHz, CDCl3) δ
58.4, 26.1, 18.6, -5.0. IR (film) 3036, 2954, 2930, 2857,
1497, 1462, 1248, 1076, 835, 780 cm-1. HRMS (ESI) m/z
calcd for C24H30KO3Si [M+K]+: 433.1601, found:
433.1597.
7.33 (s, 2H), 6.93 (s, 1H), 6.58 (d, J = 3.0 Hz, 1H), 6.33 (d,
J = 3.0 Hz, 1H), 4.74 (s, 2H), 2.37 (s, 6H), 0.97 (s, 9H),
0.16 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 153.9, 153.8,
138.2, 130.9, 129.1, 121.7, 109.4, 105.5, 58.5, 26.1, 21.5,
18.6, -5.0. IR (film) 3028, 2954, 2929, 2857, 1545, 1465,
1254, 1076, 838, 779 cm-1. HRMS (ESI) m/z Calcd for
C19H28KO2Si [M+K]+: 355.1496, found: 355.1494.
tert-Butyldimethyl((5-(m-tolyl)furan-2-
yl)methoxy)silane (2bi)
1
tert-Butyl((5-(3,5-dimethoxyphenyl)furan-2-
Yellow oil (92.2 mg, 61%). H NMR (400 MHz, CDCl3) δ
yl)methoxy)dimethylsilane (2bp)
7.55 – 7.47 (m, 2H), 7.30 – 7.25 (m, 1H), 7.10 (d, J = 7.4
Hz, 1H), 6.60 (s, 1H), 6.34 (s, 1H), 4.74 (s, 2H), 2.42 (s,
3H), 0.97 (s, 9H), 0.16 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ 153.9, 153.7, 138.3, 131.0, 128.7, 128.2, 124.5,
121.0, 109.5, 105.6, 58.5, 26.0, 21.6, 18.6, -5.0. IR (film)
3049, 2955, 2930, 2858, 1498, 1468, 1255, 1075, 838, 778
cm-1. HRMS (ESI) m/z calcd for C18H26KO2Si [M+K]+:
341.1339, found: 341.1335.
1
Yellow oil (88.6 mg, 51%). H NMR (400 MHz, CDCl3) δ
6.86 (s, 2H), 6.60 (d, J = 3.1 Hz, 1H), 6.41 (s, 1H), 6.34 (d,
J = 3.1 Hz, 1H), 4.73 (s, 2H), 3.86 (s, 6H), 0.96 (s, 9H),
0.16 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 161.2, 154.1,
153.4, 132.8, 109.5, 106.3, 102.0, 99.9, 58.5, 55.6, 26.0,
18.6, -5.0. IR (film) 3001, 2954, 2932, 2857, 1549, 1463,
1254, 1202, 1156, 1069, 838, 781 cm-1. HRMS (ESI) m/z
calcd for C19H28KO4Si [M+K]+: 387.1394, found:
387.1390.
tert-Butyl((5-(3-isopropylphenyl)furan-2-
yl)methoxy)dimethylsilane (2bj)
1
tert-Butyl((5-(3,4-dimethylphenyl)furan-2-
Yellow oil (75.8 mg, 46%). H NMR (400 MHz, CDCl3) δ
yl)methoxy)dimethylsilane (2bq)
7.57 (s, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.32 (t, J = 7.6 Hz,
1H), 7.15 (d, J = 7.6 Hz, 1H), 6.60 (d, J = 2.6 Hz, 1H),
6.33 (d, J = 2.6 Hz, 1H), 4.74 (s, 2H), 3.03 – 2.89 (m, 1H),
1.31 (d, J = 6.9 Hz, 6H), 0.97 (s, 9H), 0.16 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ 153.9, 153.9, 149.4, 131.1,
128.8, 125.6, 121.9, 121.5, 109.5, 105.6, 58.5, 34.3, 26.1,
24.1, 18.6, -5.0. IR (film) 3026, 2959, 2932, 2860, 1550,
1467, 1257, 1080, 838, 780 cm-1. HRMS (ESI) m/z calcd
for C20H30KO2Si [M+K]+: 369.1652, found: 369.1648.
1
Yellow oil (68.0 mg, 43%). H NMR (400 MHz, CDCl3) δ
7.48 (s, 1H), 7.43 (d, J = 7.8 Hz, 1H), 7.16 (d, J = 7.8 Hz,
1H), 6.54 (d, J = 2.9 Hz, 1H), 6.32 (d, J = 2.9 Hz, 1H),
4.73 (s, 2H), 2.32 (s, 3H), 2.30 (s, 3H), 0.97 (s, 9H), 0.16
(s, 6H). 13C NMR (100 MHz, CDCl3) δ 153.9, 153.6, 136.9,
135.9, 130.0, 128.8, 125.1, 121.4, 109.5, 104.9, 58.5, 26.1,
20.0, 19.7, 18.6, -5.0. IR (film) 3018, 2954, 2930, 2858,
1550, 1458, 1255, 1076, 838, 780 cm-1. HRMS (ESI) m/z
calcd for C19H28KO2Si [M+K]+: 355.1496, found:
355.1496.
tert-Butyl((5-(3-(tert-butyl)phenyl)furan-2-
yl)methoxy)dimethylsilane (2bk)
1
(5-(Benzo[d][1,3]dioxol-5-yl)furan-2-yl)methanol (2br’)
Yellow solid (34.5 mg, 32% over two steps from 1b), mp:
84-85 C. H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 8.2
Hz, 1H), 7.13 (s, 1H), 6.81 (d, J = 8.2 Hz, 1H), 6.43 (d, J =
3.2 Hz, 1H), 6.33 (d, J = 3.2 Hz, 1H), 5.96 (s, 2H), 4.63 (s,
2H). 13C NMR (100 MHz, CDCl3) δ 154.0, 153.2, 148.1,
147.2, 125.3, 117.9, 110.1, 108.7, 104.7, 104.7, 101.3, 57.7.
IR (film) 3338, 3021, 2980, 2900, 1550, 1450, 1285, 1255,
1034, 928, 862, 798 cm-1. HRMS (ESI) m/z calcd for
C12H10NaO4 [M+Na]+: 241.0477, found: 241.0472.
Yellow oil (71.4 mg, 42%). H NMR (400 MHz, CDCl3) δ
7.75 (s, 1H), 7.50 (d, J = 6.3 Hz, 1H), 7.38 – 7.29 (m, 2H),
6.60 (d, J = 2.8 Hz, 1H), 6.34 (d, J = 2.8 Hz, 1H), 4.75 (s,
2H), 1.39 (s, 9H), 0.98 (s, 9H), 0.18 (s, 6H). 13C NMR
(100 MHz, CDCl3) δ 154.1, 153.8, 151.6, 130.8, 128.5,
124.5, 121.2, 120.8, 109.5, 105.5, 58.5, 34.9, 31.5, 26.1,
18.6, -5.0. IR (film) 3028, 2958, 2932, 2859, 1546, 1468,
1254, 1076, 838, 780 cm-1. HRMS (ESI) m/z calcd for
C21H32KO2Si [M+K]+: 383.1809, found: 383.1807.
o
1
tert-Butyl((5-(3-methoxyphenyl)furan-2-
yl)methoxy)dimethylsilane (2bl)
tert-Butyldimethyl((5-(3,4,5-trimethoxyphenyl)furan-2-
yl)methoxy)silane (2bs)
1
Yellow oil (82.3 mg, 52%). H NMR (400 MHz, CDCl3) δ
7.35 – 7.22 (m, 3H), 6.83 (d, J = 7.5 Hz, 1H), 6.61 (d, J =
3.2 Hz, 1H), 6.34 (d, J = 3.2 Hz, 1H), 4.74 (s, 2H), 3.88 (s,
3H), 0.97 (s, 9H), 0.16 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ 160.0, 154.1, 153.4, 132.4, 129.8, 116.5, 113.3,
109.6, 109.1, 106.1, 58.5, 55.4, 26.1, 18.6, -5.0. IR (film)
3028, 2956, 2929, 2857, 1539, 1467, 1258, 1081, 838, 778
cm-1. HRMS (ESI) m/z calcd for C18H26KO3Si [M+K]+:
357.1288, found: 357.1285.
o
1
Colorless solid (59.2 mg, 31%), mp: 49-50 C. H NMR
(400 MHz, CDCl3) δ 6.92 (s, 2H), 6.54 (d, J = 3.2 Hz, 1H),
6.33 (d, J = 3.2 Hz, 1H), 4.73 (s, 2H), 3.94 (s, 6H), 3.89 (s,
3H), 0.96 (s, 9H), 0.16 (s, 6H). 13C NMR (100 MHz,
CDCl3) δ 153.9, 153.6, 153.4, 137.8, 126.8, 109.6, 105.4,
101.2, 61.1, 58.4, 56.3, 26.0, 18.6, -5.0. IR (film) 3018,
2932, 2857, 1550, 1497, 1245, 1129, 1077, 837, 778 cm-1.
HRMS (ESI) m/z calcd for C20H30NaO5Si [M+Na]+:
401.1760, found: 401.1756.
((5-(3-(Benzyloxy)phenyl)furan-2-yl)methoxy)(tert-
butyl)dimethylsilane (2bm)
tert-Butyl((5-(4-fluorophenyl)furan-2-
yl)methoxy)dimethylsilane (2bt)
1
Yellow oil (91.3 mg, 45%). H NMR (400 MHz, CDCl3) δ
7.49 (d, J = 7.3 Hz, 2H), 7.43 (t, J = 7.3 Hz, 2H), 7.40 –
7.29 (m, 4H), 6.90 (d, J = 6.0 Hz, 1H), 6.61 (s, 1H), 6.34 (s,
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900799
Advanced Synthesis & Catalysis
1
Yellow oil (48.2 mg, 32%). H NMR (400 MHz, CDCl3) δ
7.69 – 7.58 (m, 2H), 7.13 – 7.02 (m, 2H), 6.52 (d, J = 3.2
Hz, 1H), 6.31 (d, J = 3.2 Hz, 1H), 4.70 (s, 2H), 0.94 (s,
9H), 0.14 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 163.4,
161.0, 153.4 (d, J = 135.2 Hz), 127.5 (d, J = 3.3 Hz), 125.5
(d, J = 8.0 Hz), 115.8 (d, J = 21.9 Hz), 109.6, 105.4, 58.4,
26.0, 18.6, -5.0. 19F NMR (376 MHz, CDCl3) δ -114.52. IR
(film) 3122, 2954, 2930, 2857, 1552, 1495, 1231, 1077,
835, 778 cm-1. HRMS (ESI) m/z calcd for C17H23FNaO2Si
[M+Na]+: 329.1349, found: 329.1346.
tert-Butyldimethyl((5-(naphthalen-2-yl)furan-2-
yl)methoxy)silane (2baa)
Yellow solid (65.5 mg, 38%), mp: 46-47 oC. 1H NMR (400
MHz, CDCl3) δ 8.17 (s, 1H), 7.91 – 7.75 (m, 4H), 7.54 –
7.43 (m, 2H), 6.73 (s, 1H), 6.40 (s, 1H), 4.79 (s, 2H), 1.00
(s, 9H), 0.20 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 154.4,
153.6, 133.7, 132.8, 128.4, 128.4, 128.3, 127.9, 126.6,
126.0, 122.4, 122.1, 109.7, 106.4, 58.5, 26.1, 18.6, -5.0. IR
(film) 3057, 2953, 2930, 2857, 1542, 1464, 1254, 1075,
836, 779, 746 cm-1. HRMS (ESI) m/z calcd for
C21H26KO2Si [M+K]+: 377.1339, found: 377.1334.
tert-Butyl((5-(4-chlorophenyl)furan-2-
yl)methoxy)dimethylsilane (2bu)
(5-(m-Tolyl)furan-2-yl)methanol (2bi’)
1
Yellow oil (50.3 mg, 30%). H NMR (400 MHz, CDCl3) δ
7.58 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 6.57 (d,
J = 3.2 Hz, 1H), 6.32 (d, J = 3.2 Hz, 1H), 4.70 (s, 2H),
0.94 (s, 9H), 0.13 (s, 6H). 13C NMR (100 MHz, CDCl3) δ
154.5, 152.5, 133.0, 129.6, 129.0, 125.0, 109.6, 106.3, 58.4,
26.0, 18.6, -5.0. IR (film) 3123, 2954, 2930, 2857, 1542,
1481, 1255, 1092, 836, 781 cm-1. HRMS (ESI) m/z calcd
for C17H22ClO2Si [M-H]-: 321.1078, found: 321.1071.
Yellow solid (0.52 g, 56% over two steps from 1b), mp:
o
1
48-49 C. H NMR (400 MHz, CDCl3) δ 7.52 – 7.41 (m,
2H), 7.25 (t, J = 7.6 Hz, 1H), 7.06 (d, J = 7.5 Hz, 1H), 6.56
(d, J = 3.1 Hz, 1H), 6.34 (d, J = 3.1 Hz, 1H), 4.63 (s, 2H),
2.37 (s, 3H), 2.08 (br, 1H). 13C NMR (100 MHz, CDCl3) δ
154.3, 153.6, 138.4, 130.7, 128.7, 128.4, 124.5, 121.1,
110.0, 105.7, 57.7, 21.6. IR (film) 3287, 3126, 2923, 2867,
1547, 1481, 1206, 1017, 780, 694 cm-1. HRMS (ESI) m/z
calcd for C12H12NaO2 [M+Na]+: 211.0735, found:
211.0729.
((5-(4-Bromophenyl)furan-2-yl)methoxy)(tert-
butyl)dimethylsilane (2bv)
1
Yellow oil (58.5 mg, 32%). H NMR (400 MHz, CDCl3) δ
2-Phenyl-5-(m-tolyl)furan (3a)
7.56 – 7.45 (m, 4H), 6.59 (d, J = 3.2 Hz, 1H), 6.32 (d, J =
3.2 Hz, 1H), 4.70 (s, 2H), 0.94 (s, 9H), 0.13 (s, 6H). 13C
NMR (100 MHz, CDCl3) δ 154.5, 152.5, 131.9, 130.0,
125.3, 121.1, 109.6, 106.4, 58.4, 26.0, 18.6, -5.0. IR (film)
3123, 2954, 2930, 2857, 1545, 1476, 1255, 1074, 837, 781
cm-1. HRMS (ESI) m/z calcd for C17H22BrO2Si [M-H]-:
365.0573, found: 365.0566.
o
1
White solid (85.2 mg, 74%), mp: 82-83 C. H NMR (400
MHz, CDCl3) δ 7.73 (d, J = 7.5 Hz, 2H), 7.61 – 7.50 (m,
2H), 7.38 (t, J = 7.7 Hz, 2H), 7.32 – 7.21 (m, 2H), 7.07 (d,
J = 7.4 Hz, 1H), 6.77 – 6.64 (m, 2H), 2.39 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 153.7, 153.4, 138.4, 131.0,
130.8, 128.8, 128.7, 128.3, 127.4, 124.5, 123.8, 121.0,
107.3, 107.2, 21.6. IR (film) 3046, 2959, 1602, 1533, 1478,
1271, 1022, 772 cm-1. HRMS (ESI) m/z calcd for C17H15O
[M+H]+: 235.1123, found: 235.1115.
tert-Butyldimethyl((5-(4-(trifluoromethyl)phenyl)furan-
2-yl)methoxy)silane (2bw)
1
Yellow oil (56.3 mg, 32%). H NMR (400 MHz, CDCl3) δ
2,5-Di-m-tolylfuran (3b)
7.74 (d, J = 8.1 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), 6.70 (s,
1H), 6.36 (s, 1H), 4.72 (s, 2H), 0.94 (s, 9H), 0.14 (s, 6H).
13C NMR (100 MHz, CDCl3) δ 155.3, 152.1, 134.2, 129.0
(q, J = 32.6 Hz), 125.8 (q, J = 3.9 Hz), 124.3 (q, J = 270.0
Hz),123.74, 109.7, 107.8, 58.4, 26.0, 18.6, -5.0. 19F NMR
(376 MHz, CDCl3) δ -62.51. IR (film) 3125, 2957, 2930,
2861, 1551, 1468, 1325, 1258, 1074, 838, 752 cm-1.
HRMS (ESI) m/z calcd for C18H23F3NaO2Si [M+Na]+:
379.1317, found: 379.1316.
o
1
White solid (85.0 mg, 69%), mp: 92-93 C. H NMR (400
MHz, CDCl3) δ 7.78 – 7.58 (m, 4H), 7.38 (t, J = 7.6 Hz,
2H), 7.17 (d, J = 7.6 Hz, 2H), 6.79 (s, 2H), 2.50 (s, 6H).
13C NMR (100 MHz, CDCl3) δ 153.5, 138.4, 130.9, 128.7,
128.2, 124.4 121.0, 107.2, 21.6. IR (film) 3023, 2920,
1589, 1534, 1479, 1287, 1025, 782 cm-1. HRMS (ESI) m/z
calcd for C18H17O [M+H]+: 249.1279, found: 249.1268.
2-(m-Tolyl)-5-(p-tolyl)furan (3c)
((5-([1,1'-Biphenyl]-4-yl)furan-2-yl)methoxy)(tert-
butyl)dimethylsilane (2bx)
o
1
White solid (79.8 mg, 65%), mp: 110-111 C. H NMR
(400 MHz, CDCl3) δ 7.62 (d, J = 8.0 Hz, 2H), 7.56 – 7.49
(m, 2H), 7.26 (t, J = 7.6 Hz, 1H), 7.18 (d, J = 8.0 Hz, 2H),
7.05 (d, J = 7.5 Hz, 1H), 6.67 (d, J = 3.4 Hz, 1H), 6.63 (d,
J = 3.4 Hz, 1H), 2.38 (s, 3H), 2.34 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 153.6, 153.3, 138.4, 137.2, 130.9, 129.5,
128.7, 128.3, 128.2, 124.4, 123.8, 121.0, 107.2, 106.6, 21.6,
21.4. IR (film) 3123, 2922, 1591, 1537, 1494, 1280, 1020,
778 cm-1. HRMS (ESI) m/z calcd for C18H17O [M+H]+:
249.1279, found: 249.1270.
o
1
White solid (70.7 mg, 39%), mp: 73-74 C. H NMR (400
MHz, CDCl3) δ 7.77 (d, J = 7.8 Hz, 2H), 7.66 (d, J = 7.5
Hz, 4H), 7.48 (t, J = 7.2 Hz, 2H), 7.38 (t, J = 7.3 Hz, 1H),
6.66 (s, 1H), 6.38 (s, 1H), 4.76 (s, 2H), 1.00 (s, 9H), 0.19
(s, 6H). 13C NMR (100 MHz, CDCl3) δ 154.2, 153.3, 140.8,
140.0, 130.0, 128.9, 127.4, 127.0, 124.2, 109.7, 106.0, 58.5,
26.1, 18.6, -5.0. One of the peaks of 13C NMR may be
overlapped by others. IR (film) 3055, 2954, 2930, 2857,
1566, 1465, 1254, 1109, 838, 764 cm-1. HRMS (ESI) m/z
calcd for C23H28NaO2Si [M+Na]+: 387.1756, found:
387.1752.
2-(3-Methoxyphenyl)-5-(m-tolyl)furan (3d)
o
1
White solid (88.1 mg, 68%), mp: 81-82 C. H NMR (400
MHz, CDCl3) δ 7.66 – 7.59 (m, 2H), 7.44 – 7.32 (m, 4H),
7.15 (d, J = 7.5 Hz, 1H), 6.89 (d, J = 8.4 Hz, 1H), 6.81 –
6.73 (m, 2H), 3.91 (s, 3H), 2.47 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 160.0, 153.7, 153.1, 138.4, 132.2, 130.7,
129.9, 128.7, 128.3, 124.4, 121.1, 116.5, 112.8, 109.4,
107.7, 107.2, 55.3, 21.6. IR (film) 3055, 2955, 1591, 1537,
1484, 1288, 1217, 1025, 774 cm-1. HRMS (ESI) m/z calcd
for C18H17O2 [M+H]+: 265.1229, found: 265.1223.
Ethyl 4-(5-(((tert-butyldimethylsilyl)oxy)methyl)furan-
2-yl)benzoate (2by)
1
Yellow oil (22.8 mg, 13%). H NMR (400 MHz, CDCl3) δ
8.04 (d, J = 8.2 Hz, 2H), 7.70 (d, J = 8.2 Hz, 2H), 6.72 (d,
J = 3.0 Hz, 1H), 6.35 (d, J = 3.0 Hz, 1H), 4.72 (s, 2H),
4.38 (q, J = 7.2 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H), 0.93 (s,
9H), 0.13 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 166.5,
155.3, 152.5, 134.9, 130.2, 128.9, 123.3, 109.8, 108.0, 61.1,
58.5, 26.0, 18.6, 14.5, -5.0. IR (film) 3123, 2955, 2931,
2858, 1716, 1611, 1571, 1274, 1105, 838, 772 cm-1.
HRMS (ESI) m/z calcd for C20H28NaO4Si [M+Na]+:
383.1655, found: 383.1650.
2-(4-Methoxyphenyl)-5-(m-tolyl)furan (3e)
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900799
Advanced Synthesis & Catalysis
o
1
o
1
White solid (82.4 mg, 62%), mp: 134-135 C. H NMR
(400 MHz, CDCl3) δ 7.72 (d, J = 8.6 Hz, 2H), 7.62 – 7.55
(m, 2H), 7.33 (t, J = 7.6 Hz, 1H), 7.11 (d, J = 7.5 Hz, 1H),
6.98 (d, J = 8.6 Hz, 2H), 6.73 (d, J = 3.4 Hz, 1H), 6.62 (d,
J = 3.4 Hz, 1H), 3.86 (s, 3H), 2.45 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 159.2, 153.5, 153.0, 138.4, 131.0, 128.7,
128.1, 125.3, 124.3, 124.1, 120.9, 114.3, 107.2, 105.8, 55.4,
21.6. IR (film) 3023, 2968, 1566, 1497, 1468, 1293, 1024,
774 cm-1. HRMS (ESI) m/z calcd for C18H16O2 [M]+:
264.1150, found: 264.1142.
White solid (80.5 mg, 52%), mp: 118-119 C. H NMR
(400 MHz, CDCl3) δ 7.65 – 7.48 (m, 6H), 7.32 (t, J = 7.4
Hz, 1H), 7.13 (d, J = 7.4 Hz, 1H), 6.72 (s, 2H), 2.44 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 154.0, 152.2, 138.5,
131.9, 130.6, 129.8, 128.8, 128.5, 125.2, 124.5, 121.1,
121.0, 107.9, 107.3, 21.6. IR (film) 3021, 2917, 1606,
1531, 1476, 1282, 1023, 782 cm-1. HRMS (ESI) m/z calcd
for C17H14BrO [M+H]+: 313.0228, found: 313.0218.
2-(4-Chlorophenyl)-5-(m-tolyl)furan (3l)
o
1
2-(4-(tert-Butyl)phenyl)-5-(m-tolyl)furan (3f)
White solid (60.7 mg, 45%), mp: 113-114 C. H NMR
(400 MHz, CDCl3) δ 7.67 (d, J = 8.2 Hz, 2H), 7.60 – 7.53
(m, 2H), 7.39 (d, J = 8.2 Hz, 2H), 7.33 (t, J = 7.6 Hz, 1H),
7.13 (d, J = 7.5 Hz, 1H), 6.72 (s, 2H), 2.44 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 153.9, 152.2, 138.5, 132.9,
130.6, 129.4, 129.0, 128.8, 128.5, 125.0, 124.5, 121.1,
107.8, 107.3, 21.6. IR (film) 3022, 2921, 1606, 1531, 1476,
1282, 1023, 782 cm-1. HRMS (ESI) m/z calcd for
C17H13ClO [M]+: 268.0655, found: 268.0641.
o
1
White solid (87.0 mg, 60%), mp: 84-85 C. H NMR (400
MHz, CDCl3) δ 7.77 (d, J = 8.4 Hz, 2H), 7.67 – 7.60 (m,
2H), 7.51 (d, J = 8.4 Hz, 2H), 7.37 (t, J = 7.6 Hz, 1H), 7.16
(d, J = 7.5 Hz, 1H), 6.77 (d, J = 3.4 Hz, 1H), 6.74 (d, J =
3.4 Hz, 1H), 2.49 (s, 3H), 1.44 (s, 9H). 13C NMR (100
MHz, CDCl3) δ 153.6, 153.3, 150.5, 138.4, 131.0, 128.7,
128.3, 128.2, 125.7, 124.4, 123.7, 121.0, 107.2, 106.8, 34.7,
31.4, 21.6. IR (film) 3034, 2962, 1611, 1586, 1493, 1268,
1023, 779 cm-1. HRMS (ESI) m/z calcd for C21H23O
[M+H]+: 291.1749, found: 291.1739.
Ethyl 4-(5-(m-tolyl)furan-2-yl)benzoate (3m)
o
1
White solid (25.0 mg, 17%), mp: 120-121 C. H NMR
(400 MHz, CDCl3) δ 8.08 (d, J = 7.8 Hz, 2H), 7.79 (d, J =
7.8 Hz, 2H), 7.61 – 7.52 (m, 2H), 7.31 (t, J = 7.6 Hz, 1H),
7.12 (d, J = 7.5 Hz, 1H), 6.86 (s, 1H), 6.75 (s, 1H), 4.40 (q,
J = 7.0 Hz, 2H), 2.42 (s, 3H), 1.42 (t, J = 7.0 Hz, 3H). 13C
NMR (100 MHz, CDCl3) δ 166.5, 154.8, 152.3, 138.5,
134.7, 130.4, 130.2, 128.9, 128.8, 128.8, 124.7, 123.3,
121.3, 109.6, 107.6, 61.1, 21.7, 14.5. IR (film) 3023, 2982,
1711, 1608, 1535, 1471, 1272, 1026, 773 cm-1. HRMS
(ESI) m/z calcd for C20H19O3 [M+H]+: 307.1334, found:
2-(m-Tolyl)-5-(o-tolyl)furan (3g)
o
1
White solid (28.1 mg, 23%), mp: 59-60 C. H NMR (400
MHz, CDCl3) δ 7.78 (d, J = 7.7 Hz, 1H), 7.57 – 7.50 (m,
2H), 7.31 – 7.18 (m, 4H), 7.07 (d, J = 7.5 Hz, 1H), 6.73 (d,
J = 3.4 Hz, 1H), 6.61 (d, J = 3.4 Hz, 1H), 2.55 (s, 3H),
2.39 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 153.3, 153.1,
138.4, 134.6, 131.4, 130.9, 130.3, 128.8, 128.3, 127.5,
127.0, 126.2, 124.5, 121.1, 110.8, 106.9, 22.2, 21.7. IR
(film) 3061, 2922, 1602, 1536, 1481, 1276, 1025, 776 cm-1. 307.1331.
HRMS (ESI) m/z calcd for C18H17O [M+H]+: 249.1279,
found: 249.1270.
2-(m-Tolyl)-5-(4-(trifluoromethyl)phenyl)furan (3n)
o
1
2-(3,5-Dimethylphenyl)-5-(m-tolyl)furan (3h)
White solid (25.2 mg, 17%), mp: 129-130 C. H NMR
(400 MHz, CDCl3) δ 7.82 (d, J = 8.3 Hz, 2H), 7.65 (d, J =
8.3 Hz, 2H), 7.60 – 7.53 (m, 2H), 7.32 (t, J = 7.6 Hz, 1H),
7.13 (d, J = 7.5 Hz, 1H), 6.84 (d, J = 3.5 Hz, 1H), 6.75 (d,
J = 3.5 Hz, 1H), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 154.8, 151.8, 138.6, 134.1 (d, J = 1.4 Hz), 130.5, 129.0
(q, J = 32.2 Hz), 128.9, 128.8, 125.9 (q, J = 3.9 Hz), 124.7,
124.4 (q, J = 270.0 Hz), 123.8, 121.3, 109.4, 107.5, 21.6.
19F NMR (376 MHz, CDCl3) δ -62.47. IR (film) 3019,
2934, 1581, 1538, 1495, 1291, 1165, 1113, 1024, 783 cm-1.
HRMS (ESI) m/z calcd for C18H13F3KO [M+K]+: 341.0556,
found: 341.0762.
o
1
White solid (85.6 mg, 66%), mp: 88-89 C. H NMR (400
MHz, CDCl3) δ 7.67 – 7.60 (m, 2H), 7.45 (s, 2H), 7.36 (t, J
= 7.6 Hz, 1H), 7.15 (d, J = 7.5 Hz, 1H), 6.98 (s, 1H), 6.79
– 6.73 (m, 2H), 2.48 (s, 3H), 2.44 (s, 6H). 13C NMR (100
MHz, CDCl3) δ 153.7, 153.4, 138.4, 138.3, 130.9, 130.8,
129.2, 128.7, 128.2, 124.4, 121.7, 121.0, 107.2, 107.1, 21.6,
21.5. IR (film) 3021, 2919, 1605, 1534, 1478, 1288, 1026,
783 cm-1. HRMS (ESI) m/z calcd for C19H19O [M+H]+:
263.1436, found: 263.1426.
2-(3,5-Dimethoxyphenyl)-5-(m-tolyl)furan (3i)
2-(Naphthalen-1-yl)-5-(m-tolyl)furan (3p)
o
1
White solid (85.8 mg, 58%), mp: 77-78 C. H NMR (400
MHz, CDCl3) δ 7.61 – 7.53 (m, 2H), 7.31 (t, J = 7.6 Hz,
1H), 7.11 (d, J = 7.4 Hz, 1H), 6.94 (d, J = 2.2 Hz, 2H),
6.78 – 6.69 (m, 2H), 6.43 (t, J = 2.2 Hz, 1H), 3.88 (s, 6H),
2.43 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 161.2, 153.7,
153.1, 138.4, 132.7, 130.7, 128.7, 128.4, 124.5, 121.1,
107.9, 107.2, 102.2, 99.6, 55.5, 21.6. IR (film) 3021, 2938,
1597, 1537, 1460, 1203, 1155, 1025, 779 cm-1. HRMS
(ESI) m/z calcd for C19H19O3 [M+H]+: 295.1334, found:
295.1329.
1
Yellow oil (17.0 mg, 12%). H NMR (400 MHz, CDCl3) δ
8.54 (d, J = 8.2 Hz, 1H), 7.92 (d, J = 7.6 Hz, 1H), 7.86 (t, J
= 6.8 Hz, 2H), 7.65 – 7.52 (m, 5H), 7.33 (t, J = 7.6 Hz, 1H),
7.13 (d, J = 7.5 Hz, 1H), 6.85 (d, J = 3.4 Hz, 1H), 6.83 (d,
J = 3.4 Hz, 1H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3)
δ 154.2, 153.0, 138.5, 134.2, 130.9, 130.5, 128.8, 128.7,
128.7, 128.7, 128.4, 126.8, 126.2, 126.1, 125.7, 125.5,
124.6, 121.2, 111.6, 107.0, 21.7. IR (film) 3053, 2922,
1528, 1478, 1277, 1022, 772 cm-1. HRMS (ESI) m/z calcd
for C21H17O [M+H]+: 285.1279, found: 285.1271.
2-(4-Fluorophenyl)-5-(m-tolyl)furan (3j)
2-(Naphthalen-2-yl)-5-(m-tolyl)furan (3q)
o
1
White solid (76.7 mg, 61%), mp: 98-99 C. H NMR (400
MHz, CDCl3) δ 7.80 – 7.69 (m, 2H), 7.64 – 7.54 (m, 2H),
7.35 (t, J = 7.5 Hz, 1H), 7.20 – 7.09 (m, 3H), 6.73 (s, 1H),
6.67 (s, 1H), 2.46 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
162.2 (d, J = 246.9 Hz), 153.6, 152.5, 138.4, 130.7, 128.7,
128.3, 127.3 (d, J = 3.3 Hz), 125.50 (d, J = 8.0 Hz), 124.4,
121.0, 115.8 (d, J = 21.9 Hz), 107.2, 107.0, 21.6. 19F NMR
(376 MHz, CDCl3) δ -114.16. IR (film) 3021, 2923, 1571,
1538, 1492, 1297, 1022, 781 cm-1. HRMS (ESI) m/z calcd
for C17H13FO [M]+: 252.0950, found: 252.0938.
o
1
White solid (77.7 mg, 55%), mp: 122-123 C. H NMR
(400 MHz, CDCl3) δ 8.24 (s, 1H), 7.93 (d, J = 7.9 Hz, 1H),
7.90 – 7.81 (m, 3H), 7.69 – 7.62 (m, 2H), 7.56 – 7.45 (m,
2H), 7.36 (t, J = 7.6 Hz, 1H), 7.15 (d, J = 7.5 Hz, 1H), 6.87
(d, J = 3.5 Hz, 1H), 6.79 (d, J = 3.5 Hz, 1H), 2.47 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 154.0, 153.5, 138.5, 133.8,
132.8, 130.8, 128.8, 128.5, 128.4, 128.3, 127.9, 126.6,
126.0, 124.6, 122.4, 122.1, 121.2, 108.0, 107.4, 21.7. One
of the peaks of 13C NMR may be overlapped by others. IR
(film) 3056, 2924, 1534, 1454, 1266, 1024, 781 cm-1.
HRMS (ESI) m/z calcd for C21H17O [M+H]+: 285.1279,
found: 285.1268.
2-(4-Bromophenyl)-5-(m-tolyl)furan (3k)
8
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900799
Advanced Synthesis & Catalysis
Acknowledgements
Beauchamp, Chem. Rev. 1990, 90, 629-688; d) J.
Halpern, Acc. Chem. Res. 1982, 15, 238-244; e) M.
Murakami, N. Ishida, J. Am. Chem. Soc. 2016, 138,
13759-13769.
This work was supported by grants from the National Program
on Key Research Project (No. 2016YFA0602900), the National
Natural Science Foundation of China (Nos. 21572068 and
21871094), the Science and Technology Program of Guangzhou,
China (No. 201707010057), Guangdong Natural Science
Foundation (No. 2017A030312005), and the Science and
Technology Planning Project of Guangdong Province, China (No.
2017A020216021).
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9
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900799
Advanced Synthesis & Catalysis
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10.1002/adsc.201900799
Advanced Synthesis & Catalysis
FULL PAPER
Palladium-Catalyzed
Cross-Coupling
of
Furfuryl Alcohols with Arylboronic Acids via
Aromatization-Driven Carbon–Carbon Bond
Cleavage to Synthesize 5-Arylfurfuryl Alcohols
and 2,5-Diaryl Furans
Adv. Synth. Catal. 2019, Volume, Page – Page
Guanghao Huang, Biaolin Yin*
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