Aerobic oxidative α-arylation of furans with boronic acids via Pd(II)-catalyzed C-C bond cleavage of primary furfuryl alcohols: Sustainable access to arylfurans

Article abstract of DOI:10.1039/c7cc07111f

Aerobic oxidative α-arylation of furans with boronic acids via Pd(ii)-catalyzed C-C bond cleavage of primary furfuryl alcohols provides sustainable access to arylfurans. This protocol opens a new avenue for the transformation of readily available furans into other useful compounds.

Full text of DOI:10.1039/c7cc07111f

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Aerobic Oxidative α-Arylation of Furans with Boronic Acids via
Pd(II)-Catalyzed C–C Bond Cleavage of Primary Furfuryl Alcohols:
Sustainable Access to Arylfurans
Received 00th January 20xx,
Accepted 00th January 20xx
Guanghao Huang, Lin Lu, Huanfeng Jiang and Biaolin Yin*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Aerobic oxidative α-arylation of furans with boronic acids via alcohols affords furan oxonium ion intermediates, which can
Pd(II)-catalyzed C–C bond cleavage of primary furfuryl alcohols be transformed into an array of structures.10 In addition,
provides sustainable access to arylfurans. The protocol opens a oxidative cleavage of furfuryl alcohols produces synthetically
new avenue for the transformation of readily available furans into useful hydroxyl-substituted Z-enediones.11 Considering that
other useful compounds.
the furan ring is a good leaving group, we hypothesized that
Pd(II)-catalyzed C–C bond cleavage reactions of furfuryl
Transition-metal-catalyzed cleavage of C–C bonds allows
reorganization of bond connections and thus can facilitate the
synthesis of complex molecules of interest.1 However, cleaving
C–C bonds is usually difficult due to their inherent stability.2
Cleavage of C–C bonds in unstrained molecules is particularly
difficult because of the lack of a driving force for the reaction.
For unstrained molecules, a driving force can be provided by
incorporating a good leaving group into the substrate3 or by
alcohols
1 to form 2-furyl palladium compounds 2 would be an
excellent method for the synthesis of furan derivatives. As part
of our ongoing work on the synthetic applications of furans,12
we herein report a method for sustainable access to arylfurans
3
via aerobic oxidative α-arylation of furans with boronic acids
(Scheme 1). Arylfurans, which have interesting bioactivities
and physical properties,13 are usually synthesized via Suzuki
coupling of the corresponding halides and boronic acids.14
previous work:
using
a chelation auxiliary that stabilizes the reaction
YH
intermediate.4 For example, tertiary alcohols can undergo
catalytic selective C–C bond cleavage via β-carbon elimination
to form an organometallic intermediate and a ketone. Such
organometallic intermediates can be coupled with organic
halides,5 alkenes,6 aldehydes,7 or imines8 to produce a variety
of molecules (Scheme 1). In addition, Shi et al. recently
reported Rh(III)-catalyzed C–C bond cleavage reactions of
secondary alcohols by means of β-carbon elimination directed
by a pyridinyl group to form a five-membered rhodacycle
intermediate, which underwent further alkenylation with
various olefins.6b However, transition-metal-catalyzed C–C
bond cleavage reactions of primary alcohols have rarely been
reported.4j
Y
O
R
R'
R'
H
R1
R2
OM
R
R1
R2
R
R'
RM
R'
R'X
tertiary and secondary
alcohols
Y = O, NTs
R
R'
this work:
[Pd]
CH2OH
ArB(OH)2
R1
O
1
R1
PdAr
R1
Ar
O
O
2
3
primary alcohols
Scheme 1. Transition-metal-catalyzed C–C bond cleavage reactions of alcohols.
The success of this oxidative coupling relies on the use of
suitable substrates
1 to guarantee formation of palladium
Substituted furfuryl alcohols are readily accessible from
furfural, which is produced on a large scale by acid hydrolysis
of polysaccharide-containing plant materials, and these
alcohols are excellent five-carbon building blocks with unique
reactivities that allow the construction of numerous molecules
of interest.9 For example, acid-catalyzed hydrolysis of furfuryl
compounds 2 and the development of reaction conditions to
suppress side reactions such as oxidation of the electron-rich
furan ring, oxidation of the primary hydroxyl group, oxidation
of phenylboronic acid, β-arylation, and oligomerization of the
furan rings. We began by exploring the reaction of (5-phenyl-
furan-2-yl)-methanol (1a) with phenylboronic acid (Table 1).
Gratifyingly, in the presence of Pd(OAc)2 (10 mol %) as the
catalyst, 1,10-phenanthroline (L1, 12 mol %) as the ligand, KF
(200 mol %) as an additive, and DCE (1.5 mL) as the solvent,
reaction of 1a at 70 °C for 15 h afforded desired product 3a in
63% yield (entry 1). Screening of various other palladium
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School
of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou 510640, P. R. China. E-mail: blyin@scut.edu.cn
†Electronic Supplementary Information (ESI) available: Experimental methods,
characterization of products and NMR spectra. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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catalysts (entries 1–8) indicated the Pd(OAc)2 was optimal.
Using the optimized conditions, we explored the substrate
Examination of several bidentate nitrogen ligands (entries 9– scope of the reaction by coupling 1a with various arylboronic
14) revealed that the electronic and steric properties of the acids (Table 2). Reaction of 1a with an arylboronic acid bearing
ligand apparently influenced the reaction outcome. 2,9- an electron-donating group at the meta- or para-position
Dimethyl-1,10-phenanthroline (L2), which was sterically bulkier afforded the corresponding products (3b
–3f) in good yields
than L1, gave only a trace of 3a (entry 9). The electron- (60–70%, entries 2–6). However, the reaction of 1a with 2-
deficient ligand 1,10-phen-5,6-dione (L3) gave 3a in a very low methyl phenylboronic acid gave 3g in a very low yield (31%,
yield (27%, entry 10). The use of several 2,2'-bipyridine ligands entry 7), which indicated that the reaction was sensitive to the
led to good yields (entries 11–14), and 4,4'-dimethyl-2,2'- steric bulk of the arylboronic acid. 3,5-Dimethyl and 3,5-
bipyridyl (L7) provided the best yield (69%). Replacing KF with dimethoxyl phenylboronic acids afforded 3h and 3i in 71% and
other additives (K2CO3, KOAc, K3PO4, or CsF) did not improve 66% yields, respectively (entries 8 and 9). Arylboronic acids
the yield (entries 15–18). We were pleased to find that when that were para-substituted with an electron-withdrawing
the Pd(OAc)2 loading was reduced to 5 mol %, the yield group, such as a halogen atom, COOEt, CF3, CHO, CN, or NO2,
improved slightly to 73% (entry 19). However, further reacted with 1a to give the corresponding coupling products in
decreasing the Pd(OAc)2 loading to 2 mol % diminished the moderate to trace yields (entries 10–17). Reaction of 1a with
yield to 47% (entry 20). In the absence of either Pd(OAc)2 or 1-naphthylboronic acid gave 3r in a low yield (29%, entry 18),
the ligand, none of the desired product was obtained (entries whereas reaction with 2-naphthylboronic, which was less
21 and 22); and in the absence of KF, the yield of 3a was only sterically bulky, afforded 3s in a higher yield (52%, entry 19);
21% (entry 23). Thus, we concluded that the optimal this result confirmed again that steric hindrance had a marked
conditions for this reaction involved the use of Pd(OAc)2 (5 mol impact on the reaction outcome.
%) as the catalyst, L7 (12 mol %) as the ligand, KF (200 mol %)
Table 2 Coupling of 1a with arylboronic acidsa
as the additive, DCE as the solvent, and 70 °C as the reaction
temperature (entry 19).
Table 1 Optimization of reaction conditionsa
entry
Ar
3 (yield [%]b)
1
Ph
3a (69)
3b (68)
3c (64)
3d (70)
3e (66)
3f (60)
3g (31)
3h (71)
3i (66)
3j (55)
3k (58)
3l (33)
3m (44)
3n (21)
3o (18)
3p (9)
2
3-MeC6H4
4-MeC6H4
3-MeOC6H4
4-MeOC6H4
4-t-BuC6H4
2-MeC6H4
3,5-diMeC6H4
3,5-diMeOC6H4
4-FC6H4
entry
[Pd]
ligand
additive
yield (%)b
3
1
Pd(OAc)2
PdBr2
L1
L1
L1
L1
L1
L1
L1
L1
L2
L3
L4
L5
L6
L7
L7
L7
L7
L7
L7
L7
L7
—
L7
KF
63
62
10
15
58
44
17
56
trace
27
67
65
60
69
52
50
35
21
73
47
0
4
2
KF
5
6c
3
PdCl2
KF
4
Pd(dppf)2Cl2
Pd(CH3CN)2Cl2
Pd2(dba)3
Pd(CF3COO)2
Pd[O2C(CH3)3]2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
—
KF
7
5
KF
8
6
KF
7
KF
9
8
KF
10
11
12
13
14
15
16
17
18
19
9
KF
4-BrC6H4
10
11
12
13
14
15
16
17
18
19c
20d
21c
22c
23c
KF
4-ClC6H4
KF
4-COOEtC6H4
4-CF3C6H4
4-CHOC6H4
4-CNC6H4
4-NO2C6H4
1-Naphthyl
2-Naphthyl
KF
KF
KF
K2CO3
KOAc
K3PO4
CsF
KF
3q (trace)
3r (29)
3s (52)
KF
aReaction conditions, unless otherwise noted: 1a (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 mL), 70 °C, 15 h. bIsolated yield. c2.5 mL of DCE.
KF
Pd(OAc)2
Pd(OAc)2
KF
0
—
21
We explored the substrate scope of the reaction further by
coupling 3,5-dimethylphenylboronic acid with furfuryl alcohols
aReaction conditions, unless otherwise noted: 1a (0.2 mmol), PhB(OH)2 (0.5
mmol), Pd catalyst (10 mol %), ligand (12 mol %), additive (200 mol %), O2 (in a
balloon), DCE (1.5 mL), 70 °C, 15 h. bIsolated yield. c5 mol % Pd catalyst was used.
d2 mol % Pd catalyst was used.
1
bearing various substituents (R1–R3, Table 3). The nature of
the substituents played an important role in the reaction
outcome. When R2 and R3 were H and R1 was a phenyl group
with an electron-donating para-methyl or para-methoxyl
group, the corresponding products (3t and 3u) were obtained
2 | J. Name., 2012, 00, 1-3
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in good yields (76% and 82%, respectively; entries 1 and 2). In c), indicating that the hydroxyl group facilitated the C-C bond
contrast, when R1 had an electron-withdrawing para-nitro cleavage.
group or para-fluorine atom, the yields of the corresponding
products were lower (entries 3 and 4), presumably as a result
of the lower electron density of the furan rings. A substrate
with a thienyl group at R1 afforded 3x in 47% yield, and when
R1 was methyl or ethyl, 3y or 3z, respectively, was produced in
a relatively low yield (entries 6 and 7). Notably, when furfuryl
alcohol itself (R1–R3 = H) was employed as the substrate, a
complicated mixture of products formed, and only a trace
amount of 3a’ was isolated (entry 8). Compound 1j, with an
electron-withdrawing methoxycarbonyl substituent at R1 failed
to give the corresponding product (3b’, entry 9), perhaps
because of the low electron density of the furan ring.
Ph
Ph
Ph
CHO
O
4
3h (7%)
3h (7%))
(a)
(b)
(c)
B(OH)
2
COOH
OMe
O
standard conditions
5
Me
Me
O
1p
3h (9%)
Standard conditions: 4 or 5, or 1p (0.2 mmol), PhB(OH) (0.5 mmol), Pd(OAc) (5
2
2
o
7
mol %), L (12 mol %), KF (200 mol %), O (in a balloon), DCE (1.5 mL), 70 C,
2
15 h. Isolated yield based on 4 or 5, or 1p.
Scheme 2 Control experiments.
With R1 = Ph, substrates with various R2 and R3 groups (1k
–
On the basis of the results reported above, as well as
previously reported results on C–C bond cleavage reactions of
alcohols via β-carbon elimination,5–8 we propose the
mechanism shown in Scheme 3. The palladation of furfuryl
1o) were also examined (entries 10–14). In the reactions of
secondary alcohols, increasing the steric bulk around the
hydroxyl group decreased the yield (1k
> 1l > 1m > 1n).
Tertiary alcohol 1o gave only a very low yield of 3h (8%).
alcohols
react with the boronic acid via release of HOAc to give
Transmetallation of followed by electrophilic palladation of
the furan ring leads to , which then undergoes aromatization-
driven C–C bond cleavage to afford 10. A reductive elimination
1 with Pd(OAc)2 produces Pd complexes 6, which
Table 3 Coupling of 3,5-dimethylphenylboronic acid with furfuryl alcohols 1a
7.
7
9
reaction of 10 leads to products 3 and Pd(0). Oxidation of Pd(0)
to Pd(II) by O2 completes the catalytic cycle.15
3
3
entry
1
(yield
(%)b)
entry
1
(yield
(%)b)
3a´
(trace
)
3t
(76)
1
2
3
4
5
6
7
8
3u
(82)
3b´
9
(NDd)
3v
(62)
3h
(55)
10
11
12
13
14
3w
(63)
3h
(51)
3x
(47)
3h
(17)
3y
3h
(43)c
(NDd)
Scheme 3 Proposed reaction mechanism.
3z
3h
(8)
In summary, we have developed
a simple, practical
(27)c
protocol for the synthesis of arylfurans from sustainably
produced substituted furfuryl alcohols. This protocol involves a
novel palladium-catalyzed oxidative coupling reaction between
commercially available boronic acids and α-hydroxyalkylfurans
with O2 as the terminal oxidant, as well as a C–C bond cleavage
reaction, which may be induced by aromatization. The
protocol opens a new avenue for the transformation of readily
available furans into other useful compounds and may
facilitate the design of new reactions of furans. Further
exploration of the reaction scope, coupling partners, and
mechanism are underway in our laboratory.
aReaction conditions, unless otherwise noted: 1 (0.5 mmol), 3,5-diMeC6H4B(OH)2
(1.25 mmol), Pd(OAc)2 (5 mol %), L7 (12 mol %), KF (200 mol %), O2 (in a balloon),
DCE (1.5 mL), 70 °C, 15 h. bIsolated yield. cYield determined by 1H NMR
spectroscopy of the crude products with dibromomethane as an internal
standard. dND = not detected.
To gain insight into the mechanism of the oxidative
coupling, three control experiments was conducted (Scheme
2). Specifically, under the standard conditions, coupling of the
aldehyde
not afford product 3h in considerable yields (reaction a and b),
which indicated that and were not the main intermediate.
4 or acid 5 with 3,5-dimethylphenylboronic acid did
This work was supported by grants from the National
Program on Key Research Project (no. 2016YFA0602900), the
National Natural Science Foundation of China (no. 21572068),
the Science and Technology Program of Guangzhou, China (no.
4
5
Substrate 1p, which lacked a hydroxyl group, afforded only a
low yield (9%) of the C–C bond cleavage product 3h (reaction
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201707010057), Guangdong Natural Science Foundation
(2017A030312005) and the Science and Technology Planning
Hayashi, K. Hirano, H. Yorimitsu and K. Oshima, Chem. - Asian
J., 2008, 3, 119-125.
(a) M. Sai, H. Yorimitsu and K. Oshima, Angew. Chem., Int. Ed.,
2011, 50, 3294-3298; (b) X, S. Zhang, Y. Li, H. Li, K. Chen, Z, Q.
Lei and Z. J. Shi, Chem. - Eur. J., 2012, 18, 16214-16225.
(a) M. J. Palframan and G. Pattenden, Chem. Commun., 2014,
50, 7223-7242; (b) H. D. Hao and D. Trauner, J. Am. Chem.
Soc., 2017, 139, 4117-4122; (c) J. N. Chheda, Y. R. Leshkov
and J. A. Dumesic, Green Chem., 2007, 9, 342-350; (d) H. B.
Zhao, J. E. Holladay, H. Brown and Z. C. Zhang, Science, 2007,
316, 1597-1600.
，
Project of Guangdong Province, China (no. 2017A020216021,
2014A020221035).
8
9
Conflicts of interest
There are no conflicts to declare.
10 For selected examples, see: (a) G. Piancatelli, A. Scettri and S.
Barbadoro, Tetrahedron Lett., 1976, 17, 3555-3558; (b) G. K.
Veits, D. R. Wenz and J. Read de Alaniz, Angew. Chem., Int.
Ed., 2010, 49, 9484-9487; (c) L. I. Palmer and J. Read de Alaniz,
Angew. Chem., Int. Ed., 2011, 50, 7167-7170; (d) Y. Cai, Y.
Tang, I. Atodiresei and M. Rueping, Angew. Chem., Int. Ed.,
2016, 55, 14126-14130; (e) J. Xu, Y. Luo, H. Xu, Z. Chen, M.
Miao and H. Ren, J. Org. Chem., 2017, 82, 3561-3570; (f) S.
Roscales and A. G. Csákÿ, Chem. Commun., 2016, 52, 3018-
3021.
Notes and references
1
For selected reviews on transition-metal-catalyzed cleavage
of C–C bonds, see: (a) R. H. Crabtree, Chem. Rev., 1985, 85
245-269; (b) C. H. Jun, Chem. Soc. Rev., 2004, 33, 610-618; (c)
M. Murakami and T. Matsuda, Chem. Commun., 2011, 47
,
,
1100-1105; (d) F. Chen, T. Wang and N. Jiao, Chem. Rev.,
2014, 114, 8613-8661; (e) L. Souillart and N. Cramer, Chem.
Rev., 2015, 115, 9410-9464; (f) M. Murakami and N. Ishida, J.
Am. Chem. Soc., 2016, 138, 13759-13769.
11 For selected reviews, see: (a) J. Deska, D. Thiel and E. Gianolio,
Synthesis, 2015, 47, 3435-3450; (b) A. K. Ghosh and M.
2
3
For selected examples on the intrinsic difficulties of C–C bond
cleavage, see: (a) J. Halpern, Acc. Chem. Res., 1982, 15, 238-
244; (b) P. E. M. Siegbahn and M. R. A. Blomberg, J. Am.
Chem. Soc., 1992, 114, 10548-10556.
For selected examples, see: (a) S. M. Bonesi and M. Fagnoni,
Chem. - Eur. J., 2010, 16, 13572-13589; (b) S. M. Bonesi, M.
Brindisi, RSC Adv., 2016,
examples, see: (c) O. Achmatowicz, P. Bukowski, B. Szechner,
Z. Zwierzchowska and A. Zamojski, Tetrahedron, 1971, 27
6, 111564-111598; For selected
,
1973-1996; (d) D. Noutsias, I. Alexopoulou, T. Montagnon and
G. Vassilikogiannakis, Green Chem., 2012, 14, 601-604; (e) Z.
Li and R. Tong, J. Org. Chem., 2016, 81, 4847-4855; (f) M. B.
Plutschack, P. H. Seeberger and K. Gilmore, Org. Lett., 2017,
19, 30-33.
Fagnoni and A. Albini, Angew. Chem., Int. Ed., 2008, 47
,
10022-10025; (c) Y. Nakao, Catalytic C–CN Bond Activation,
ed. G. Dong, C-C Bond Activation; Topics in Current Chemistry
346, Springer-Verlag, Berlin, Heidelberg, 2014, pp 33−58; (d)
12 (a) B. Yin, J. Lai, Z. Zhang and H. Jiang, Adv. Synth. Catal.,
2011, 353, 1961-1965; (b) B. Yin, G. Zeng, C. Cai, F. Ji, L.
Huang, Z. Li and H. Jiang, Org. Lett., 2012, 14, 616-619; (c) B.
Yin, L. Huang, X. Wang, J. Liu and H. Jiang, Adv. Synth. Catal.,
2013, 355, 370-376; (d) B. Yin, X. Zhang, J. Liu, X. Li and H.
Jiang, Chem. Commun., 2014, 50, 8113-8116; (e) B. Yin, X.
Zhang, X. Zhang, H. Peng, W. Zhou, B. Liu and H. Jiang, Chem.
Commun., 2015, 51, 6126-6129; (f) J. Liu, X. Zhang, H. Peng,
H. Jiang and B. Yin, Adv. Synth. Catal., 2015, 357, 727-731; (g)
F. Ji, H. Peng, X. Zhang, W. Lu, S. Liu, H. Jiang. B. Liu and B. Yin,
J. Org. Chem., 2015, 80, 2092-2102; (h) H. Peng, J. Li, F. Wang,
B. Liu and B. Yin, J. Org. Chem., 2016, 81, 4939-4946; (i) J. Li,
H. Peng, F. Wang, X. Wang, H. Jiang and B. Yin, Org. Lett.,
2016, 18, 3226-3229; (j) B. Yin, C. Cai, G. Zeng, R. Zhang, X. Li
and H. Jiang, Org. Lett., 2012, 14, 1098-1101; (k) J. Li, L. Lu, Q.
H. Liu, M. Feng and X. Jiang, Chem. - Asian J., 2014, 9, 3360-
3389.
4
For selective reviews, see: (a) C. H. Jun, C. W. Moon and D. Y.
Lee, Chem. - Eur. J., 2002, , 2422-2428; (b) Y. J. Park, J. W.
Park and C. H. Jun, Acc. Chem. Res., 2008, 41, 222-234; (c) A.
Dermenci, J. W. Coe and G. Dong, Org. Chem. Front., 2014,
8
1,
567-581; For selective examples, see: (d) J. W. Suggs and C. H.
Jun, J. Am. Chem. Soc., 1984, 106, 3054-3056; (e) S. Y. Liou,
M. E. van der Boom and D. Milstein, Chem. Commun., 1998,
687-688; (f) Y. Xia, G. Lu, P. Liu and G. Dong, Nature, 2016,
539, 546-550; (g) K. Chen, H. Li, Z. Q. Lei, Y. Li, W. H. Ye, L. S.
Zhang, J. Sun and Z. J. Shi, Angew. Chem., Int. Ed., 2012, 51
9851-9855; (h) K. Chen, H. Li, Y. Li, X. S. Zhang, Z. Q. Lei and Z.
J. Shi, Chem. Sci., 2012, , 1645-1649; (i) J. Wang, W. Chen, S.
,
3
Zou, L. Liu, X. Zhang and J. Wang, Angew. Chem., Int. Ed.,
2012, 51, 12334-12338; (j) X. Yu, J. Wang, W. Guo, Y. Tian and
J. Wang, Organometallics, 2016, 35, 1876-1884.
Pan, Y. Ren, B. Liu and B. Yin, Adv. Synth. Catal., 2017, 359
,
2001-2007; (l) J. Liu, H. Peng, L. Lu, X. Xu, H. Jiang and B. Yin,
Org. Lett., 2016, 18, 6440-6443; (m) J. Liu, H. Peng, Y. Yang,
H. Jiang and B. Yin, J. Org. Chem., 2016, 81, 9695-9706.
13 (a) D. W. Boykin, A. Kumar, J. Spychala, M. Zhou, R. J.
Lombardy, W. D. Wilson, C. C. Dykstra, S. K. Jones, J. E. Hall, R.
R. Tidwell, C. Laughton, C. M. Nunn and S. Neidle, J. Med.
Chem., 1995, 38, 912-916; (b) R. B. de Oliveira, E. M. de
Souza-Fagundes, H. A. J. Siqueira, R. S. Leite, C. L. Donnici and
C. L. Zani, Eur. J. Med. Chem., 2006, 41, 756-760; (c) F. Klukas,
A. Grunwald, F. Menschel and T. J. J. Müller, Beilstein J. Org.
Chem., 2014, 10, 672–679.
5
(a) Y. Terao, H. Wakui, T. Satoh, M. Miura and M. Nomura, J.
Am. Chem. Soc., 2001, 123, 10407-10408; (b) T. Nishimura, S.
Matsumura, Y. Maeda, and S. Uemura, Chem. Commun.,
2002, 50-51; (c) S. Hayashi, K. Hirano, H. Yorimitsu and K.
Oshima, J. Am. Chem. Soc., 2006, 128, 2210-2211; (d) S. L.
Zhang and Z. L. Yu, J. Org. Chem., 2016, 81, 57-65; (e) A.
Yokooji, T. Satoh, M. Miura and M. Nomura, Tetrahedron,
2004, 60, 6757-6763.
(a) T. Nishimura, H. Araki, Y. Maeda and S. Uemura, Org. Lett.,
2003, 5, 2997-2999; (b) H. Li, Y. Li, X. S. Zhang, K. Chen, X.
Wang and Z, J. Shi, J. Am. Chem. Soc., 2011, 133, 15244-
15247; (c) M. Jang, S. Hayashi, K. Hirano, H. Yorimitsu and K.
Oshima, Tetrahedron Lett., 2007, 48, 4003-4005.
6
7
14 (a) Y. Gong and H. W. Pauls, Synlett., 2000, 6, 829-831; (b) M.
Feuerstein, H. Doucet and M. Santelli, Tetrahedron Lett., 2001,
42, 5659-5662; (c) M. A. Raheem, J. R. Nagireddy, R. Durham
and W. Tam, Synthetic Commun., 2010, 40, 2138-2146.
15 (a) S. S. Stahl, J. L. Thorman, R. C. Nelson and M. A. Kozee, J.
Am. Chem. Soc., 2001, 123, 7188-7189; (b) C. R. Landis, C. M.
Morales and S. S. Stahl, J. Am. Chem. Soc., 2004, 126, 16302-
16303.
(a) Y. Takada, S. Hayashi, K. Hirano, H. Yorimitsu and K.
Oshima, Org. Lett., 2006, 8, 2515-2517; (b) H. Miura, K.
Wada, S. Hosokawa, M. Sai, T. Kondo, M. Inoue, Chem.
Commun., 2009, 4112-4114; (c) Y. Sumida, Y. Takada, S.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C7CC07111F
2
R
Pd(OAc) (5 mol %), L (12 mol %)
2
+
1
1
3
ArB(OH)
2
O
R
Ar
R
R
O
o
KF (2.0 equiv), DCE, O (balloon), 70
C
(2.5 equiv)
2
OH
33 examples
yields up to 82%
Aerobic oxidative αꢀarylation of furans with boronic acids via Pd(II)ꢀcatalyzed C–C
bond cleavage of primary furfuryl alcohol provides sustainable access to arylfurans
.