Auto-Tandem Catalysis-Induced Synthesis of Trisubstituted Furans through Domino Acid-Acid-Catalyzed Reaction of Aliphatic Aldehydes and 1,3-Dicarbonyl Compounds by using N-Bromosuccinimide as Oxidant

Article abstract of DOI:10.1002/adsc.201700074

A simple aluminium(III) chloride-catalyzed synthesis of tri-substituted furans from aliphatic aldehydes and 1,3-dicarbonyl compounds was developed by using N-bromosuccinimide (NBS) as an oxidant. This method was effective for the synthesis of various furan derivatives. Some of the products were not accessible with the previously reported methods. Mechanically, this reaction involved an auto-tandem catalysis based on a newly reported acid-acid-catalyzed tandem reaction to ensure that furans were successfully synthesized. (Figure presented.).

Full text of DOI:10.1002/adsc.201700074

COMMUNICATIONS
DOI: 10.1002/adsc.201700074
Auto-Tandem Catalysis-Induced Synthesis of Trisubstituted
Furans through Domino Acid-Acid-Catalyzed Reaction of
Aliphatic Aldehydes and 1,3-Dicarbonyl Compounds by using
N-Bromosuccinimide as Oxidant
Wenbo Huang,a Changhui Liu,a,* and Yanlong Gua,b,*
a
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key
Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong
University of Science and Technology, 1037 Luoyu road, Hongshan District, Wuhan 430074, Peopleꢀs Republic of China
Fax : (+86)-27-8754-4532; phone: (+86)-27-8754-37 32; e-mail: liuch915@hust.edu.cn or klgyl@hust.edu.cn
b
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Lanzhou
730000, Peopleꢀs Republic of China
Received: January 19, 2017; Revised: February 16, 2017; Published online: && &&, 0000
Supporting information for this article can be found under http://dx.doi.org/10.1002/adsc.201700074.
Abstract: A simple aluminium(III) chloride-cata-
lyzed synthesis of tri-substituted furans from ali-
phatic aldehydes and 1,3-dicarbonyl compounds
was developed by using N-bromosuccinimide
(NBS) as an oxidant. This method was effective for
the synthesis of various furan derivatives. Some of
the products were not accessible with the previously
reported methods. Mechanically, this reaction in-
volved an auto-tandem catalysis based on a newly
reported acid-acid-catalyzed tandem reaction to
ensure that furans were successfully synthesized.
lysts promoting a bromination reaction with NBS,[4]
we proposed the feasibility of designing an ATC
system that involves a bromination with NBS as a key
step of this reaction. Once established, this system
likely avoids the isolation of a toxic bromo-substitut-
ed product and thus simplifies the operational proce-
dure.
Polyfunctionalized furans constitute an important
class of five-membered oxygen heterocycles with
widespread applications.[5] Furan skeletons are found
in natural products possessing diverse biological activ-
ities.[6] Oligomers of furans have also been extensively
investigated because of their potential uses in materi-
als science.[7] Some furan derivatives have also been
widely recognized as useful intermediates in organic
synthesis.[8] Therefore, furans are very potential syn-
thetic targets in the search for efficient and selective
synthetic methods. Consequently, various methods
Keywords: acid catalysis; auto-tandem catalysis;
furans; N-bromosuccinimide; tandem reaction
With advancements in auto-tandem catalysis (ATC), have been developed to synthesize polysubstituted
various synthetic methodologies for heterocycles have furans.[9]
been developed.[1] Fogg and dos Santos were the first
1,3-Dicarbonyl compounds are often used as start-
to define ATC as the catalysis of multiple, mechanisti- ing substrates to synthesize furans because they are
cally distinct processes in a synthetic sequence.[2] readily available and compatible with many reaction
ATC-based synthetic protocols help us to avoid the partners. For example, the Feist–Bꢁnary reaction in-
need to store and transport harmful chemicals. It also volves the condensation of b-keto esters and a-halo
enables the use of less chemicals, the genration of less ketones under basic conditions.[10] A sequential prop-
waste, and the simplification of operational proce- argylation/cycloisomerization tandem reaction of
dures. On the other hand, bromo-substituted organic propargylic alcohols and 1,3-dicarbonyl compounds
compounds generated by using NBS as a brominating has been employed to synthesize fully substituted
reagent are widely used as synthetic intermediates.[3] furans.[11] Simple or brominated terminal alkynes have
However, most of these compounds are lachrymatory also been used as reaction partners of 1,3-dicarbonyl
and can cause many health hazards to humans. Con- compounds to synthesize furans.[12] Similar reactions
sidering the versatile reactivity of the bromo-substi- have also been extended to b-functionalized styrenes
tuted organic compounds and the diversity of cata- or allenes.[13] Other bifunctional reagents, such as al-
Adv. Synth. Catal. 0000, 000, 0 – 0
1
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
Table 1. Optimization of the reaction conditions.[a]
kynoates,[14] acyloins,[15] b-nitroacrylates,[16] a,b-unsatu-
rated ketones,[17] formylcyclopropane-1,1-diesters,[18]
2,3-dibromo-1-propenes,[19] enynes,[20] and but-2-yne-
1,4-diols,[21] have also been used in conjunction with
1,3-dicarbonyl compounds to synthesize furans. 1,3-
Dicarbonyl compounds have also been applied as sub-
strates for indirect methods.[22] Nevertheless, these
methods suffer from several limitations, such as multi-
step synthesis of the reaction partners; the use of ex-
pensive catalysts, ligands, or additives; low product
yields; poor substrate generality; and harsh condi-
tions. Therefore, the design of related approaches
should be improved to synthesize furans from readily
available precursors rapidly and cost effectively.
Entry
Catalyst
Additive
Yield [%]
1
2
3
AlCl3
AlCl3
–
–
<5
88
NR
trace
trace
36
80
68
52
56
<5
22
46
48
18
35
55
60
76
NBS
NBS
4
5
6
7
FeCl3·6H2O
PTSA
Sc(OTf)3
ZnCl2
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
NBS
NBS
NBS
NBS
I2
NCS
DDH
MnO2
NBS (30 mol%)
NBS (60 mol%)
NBS
NBS
NBS
NBS
NBS
In this study, trisubstituted furans were synthesized
from two readily available precursors, namely, aliphat-
ic aldehydes and 1,3-dicarbonyl compounds, by using
8
9[b]
10[c]
NBS as an oxidant via a simple methodology. This 11
12
13
methodology was established on the basis of an acid-
induced auto-tandem catalysis mechanism. Thus,
furans were successfully synthesized through a newly
reported acid-acid-catalyzed tandem reaction.
14[d]
15[e]
16[f]
17[g]
18[h]
19[i]
The reaction of n-amylaldehyde 1a and acetylace-
tone 2a was initially examined to investigate the feasi-
bility of using an aldehyde as a reaction partner of
1,3-dicarbonyl compounds for the synthesis of tri-sub-
stituted furans (Table 1). The reaction was performed
in acetonitrile. In the absence of a catalyst, no reac-
tion occurred. The addition of AlCl3 to the reaction
system resulted in the rapid consumption of 1a and 2a
(entry 1). However, the reaction exhibited no selectiv-
ity because many spots could be detected through
thin layer chromatography. Interestingly, a furan
product 3a was isolated with 88% yield when
1.0 equivalent of NBS was added (entry 2), but NBS
could not catalyze this transformation alone (entry 3).
This result implied that this transformation required
NBS
[a]
Reaction conditions: 1a: 0.6 mol, 2a: 0.5 mol, acetonitrile:
1 mL, catalyst: 0.025 mmol, 808C, 2 h.
NCS is N-chlorosuccinimide.
DDH is 1,3-dibromo-5,5-dimethylhydantoin.
Using AlCl3 2 mol%.
At 508C.
For 1 h.
Solvent: toluene.
Solvent: nitromethane.
[b]
[c]
[d]
[e]
[f]
[g]
[h]
[i]
Solvent: dichloroethane.
an acid catalyst. Many Lewis and Brønsted acids were played an important role in this reaction. Among var-
then examined in the presence of NBS. Our results ious solvents tested in this study, acetonitrile was the
revealed that FeCl3·6H2O and p-toluenesulfonic acid most efficient in producing the desired product 3a
(p-TsOH) were unsuitable for this reaction (entries 4 with the highest yield (88%). Toluene, nitromethane,
and 5). The reaction selectivity decreased significantly and chlorobenzene also generated high yields of 3a
when Sc(OTf)3 was used, and 3a was obtained with (55–76%) (entries 17–19). Therefore, the optimized
36% yield (entry 6). ZnCl2 showed a quite good cata- reaction conditions were as follows: 5 mol% of AlCl3
lytic performance for this transformation, and the as a catalyst, 1.0 equiv. of NBS as an additive, acetoni-
yield reached 80% (entry 7). Other halogenating re- trile as a solvent, at 808C for 2 h.
agents were also evaluated as additives by using AlCl3
The scope of this furan synthesis protocol was in-
as a catalyst. Iodine, N-chlorosuccinimide (NCS), and vestigated under the optimized reaction conditions.
1,3-dibromo-5,5-dimethylhydantoin showed a relative- The substrate scope of the aldehyde component was
ly lower efficiency than NBS, and the yields of 3a first examined (Figure 1). The reactions of linear ali-
reached 68%, 52%, and 56%, respectively (entries 8– phatic aldehydes containing either a short or long
10). MnO2, a commonly used oxidant, was also exam- carbon chain performed well and thus generated
ined. The reaction proceeded non-selectively possibly furan products with good to excellent yields (3b–3d,
because of the inappropriate activity of MnO2 3j). Aliphatic aldehydes with a benzyl or allyl group
(entry 11). The reaction yield decreased remarkably at the b-position participated readily in this reaction
as the amount of NBS decreased (entries 12 and 13). without any structural damage (3e–3h). The thiometh-
Further investigation revealed that solvents also yl and cyano groups in the aldehyde component could
Adv. Synth. Catal. 0000, 000, 0 – 0
2
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
Figure 1. Substrate scope of the furan synthesis from aldehydes and 1,3-dicarbonyl compounds.
Adv. Synth. Catal. 0000, 000, 0 – 0
3
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
also be delivered uneventfully (3i and 3am). Various
phenylacetaldehydes were then used. The expected 5-
aryl-substituted furan derivatives 3p–3aj could be syn-
thesized with a generally good yield. Although a nega-
tive effect of the electron-withdrawing nitro group
could be clearly observed when 4-nitrophenylacetal-
dehyde was utilized, the desired product 3t could be
obtained in 52% yield. Phenylacetaldehyde congeners
with naphthalene or thiophenes ring also participated
Scheme 1. Synthesis of 3an.
Notably, the reaction could be scaled up to a reac-
readily in this reaction and produced the target C-5 tion with 75 grams of starting materials without a sig-
aryl-substituted furan derivatives in excellent yield nificant loss of efficiency. In this case, the generated
(3v and 3w). Furans were also successfully synthesized by-product hydrogen bromide could be clearly detect-
by using some acetals as substrates (3ak–3am).
ed and thus be neutralized during the work-up proce-
The substrate scope of 1,3-dicarbonyl components dure (see the Supporting Information). As shown in
was then investigated. Many 1,3-dicarbonyl com- Scheme 2, the reaction of propionaldehyde 1c
pounds with ester, ether, and amide moieties were (0.43 mol) with methyl 3-oxobutanoate 2c (0.43 mol)
confirmed to be viable substrates (3i–3m). Double generated the corresponding product 3ao with 91%
and triple bonds in the molecular structure of 1,3-di- GC yield. Because the reaction was very clean, 3ao
carbonyl compounds can also be retained (3z and could be isolated with 71% yield through distillation
3aa). However, a large group in the 1,3-dicarbonyl (see the photo in Scheme 2).
component subtly influences the reaction per-
formance. For example, the 3-cyclopropyl- or 3-
phenyl-substituted 1,3-dicarbonyl compound was
rather reluctant to participate in the reaction (3ad
and 3ae). This finding might have resulted from
a steric hindrance effect. Although an insufficient re-
action occurred, the desired products could be synthe-
sized in moderate yields with these substrates. Consid-
ering that a cyclopropane scaffold is suitable for many
transformations,[23] we concluded that the proposed
reaction was quite interesting. A furan-substituted
1,3-dicarbonyl compound also readily participated in
this transformation, and the expected product 3ah
was obtained in 64% yield. In addition to the linear
1,3-dicarbonyl compound, 1,3-cyclohexandione was
applicable to this reaction (3aj). 1,3-Dicarbonyl com-
pounds could also be replaced with highly nucleophil-
ic C–H acids, such as 4-hydroxycoumarin and 4-hy-
Scheme 2. Large-scale synthesis of 3ao.
droxy-1-methyl-2-quinolone, and some fused furan
derivatives (3n and 3o) were produced through the es-
tablished reactions. These results demonstrate that
this protocol provides a convenient and practical way cidate the mechanism of this reaction and understand
to construct the furan scaffold. the exact role of AlCl3 and NBS in this reaction
Ethyl 5-(tert-butyl)-2-methylfuran-3-carboxylate (Scheme 3). Aldehyde 1b was treated with 1,3-dicar-
Various control experiments were performed to elu-
3an is a key intermediate in the synthesis of a gluca- bonyl compound 2b under the mediation of AlCl3 and
gon antagonist agent.[24] Chen et al.[25] found that the NBS. The Knoevenagel condensation product 4a was
biological activity of 3an increases when the ester formed as expected in the presence of AlCl3. Howev-
group was functionalized by a pyrazole group. How- er, NBS failed to initiate this reaction [Eq. (1)]. With
ever, the synthesis of 3an is difficult and limited by NBS treatment, 4a could be converted into its bromi-
expensive metal catalysts, starting material pre-func- nation product 5a with 90% yield. In this reaction,
tionalization, and unsatisfactory synthetic efficien- a furan derivative 3an was also formed with 8% yield
cy.[26] Using the proposed protocol for the synthesis of [Eq. (2)]. No product was detected on treating 4a
furan derivative, we developed a new way to synthe- with an AlCl3 catalyst [Eq. (3)]. Nevertheless, AlCl3
size 3an from two readily available precursors 1b and played an important role in initiating the transforma-
2b. The reaction proceeded with almost quantitative tion of 5a to 3an. The same reaction proceeded slowly
conversion and selectivity, and the yield of 3an under identical conditions when either NBS or succin-
reached 91% (Scheme 1).
ACHTUNGTRENNiUNG mide was used as a catalyst (Eq. (4)].
Adv. Synth. Catal. 0000, 000, 0 – 0
4
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
rapidly converted to a brominated intermediate II in
the presence of NBS.[27] An intramolecular oxo-Mi-
chael addition of II occurred and caused the forma-
tion of a dihydrofuran intermediate III. A furan prod-
uct was finally formed through the dehydrobromina-
tion of III. In this process, AlCl3 acted as a catalyst to
promote the following steps: (i) Knoevenagel conden-
sation of the two precursors of the reaction and (ii)
sequential intramolecular oxo-Michael and dehydro-
bromination reaction. However, NBS worked as an
allylic bromination reagent in the formation step of
II. The intervention of acid catalysis may also occur
in this step, but insufficient evidence is currently
available.[28] The present reaction system was estab-
lished on the basis of an auto-tandem catalysis of
AlCl3, which initiated a domino acid-acid-catalyzed
reaction. Thus, the final furan product was formed.
Styrene oxide 6a was found to be an alternative re-
agent to the aldehyde component in this reaction. The
desired product 3x, a furan derivative, was obtained
in 83% yield under the catalysis of AlCl3 in the pres-
ence of NBS. The initial event of the reaction was
likely an AlCl3-catalyzed reaction of 6a and 1,3-dicar-
bonyl compound 2c, which provided an intermediate
IV. Similar to this mechanism, IV underwent a bromi-
nation reaction with NBS and an acid-catalyzed se-
quential intramolecular oxo-Michael and dehydrobro-
mination reaction to generate the final product 3x
(Scheme 4).
Scheme 3. Control experiments.
A plausible reaction mechanism based on these
control experiments is depicted in Figure 2. A Knoe-
venagel condensation initially occurred between alde-
hyde and 1,3-dicarbonyl compound and thus resulted
in the formation of an intermediate I. Then, I was
Scheme 4. Reaction of styrene oxide 6a and methyl acetyl-
AHCTUNGTRENNGaUN cetate 2c.
Masked aldehydes are important building blocks
that have been widely used to synthesize heterocy-
cles.[29] Some of them could also be applied to this
transformation. In Scheme 5, 2,5-dimethoxytetrahy-
drofuran 7a, 6-methoxy-3,4-dihydro-2H-pyran 9a,
multi-substituted dihydrofuran 11a, and 2-butoxy-3,4-
dihydropyran 13a could react with 1,3-dicarbonyl
compounds. The first two compounds reacted with
2 equiv. of 1,3-dicarbonyl compounds and thus gener-
Figure 2. Plausible mechanism.
Adv. Synth. Catal. 0000, 000, 0 – 0
5
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
Scheme 5. Synthesis of furans from some masked aldehydes.
ated symmetrical bifuran derivatives 8a and 10a with
a good yield. These derivatives possess promising
physical properties.[30] Bifurans 8a and 10a can also be
considered as dicarboxylic acid esters, which can be
applied in polymer chemistry.[31] The furan derivatives
12a and 14a could be obtained when the dihydrofuran
11a and the dihydropyran 13a were used. These prod-
ucts contain a fragment of a 1,3-dicarbonyl com-
pound. Thus, these furan derivatives can be modified
in terms of the reactivity of the 1,3-dicarbonyl moiety.
2-Heptyl-5-hexylfuran-3-carboxylic acid (HHCA,
18a) has been recently isolated from a fermentation
broth of Pseudomonas sp. SJT25. This compound ex-
hibits a remarkable anti-phytopathogenic activity.[32]
However, synthesis methods for 18a have yet to be
Scheme 6. Total synthesis of HHCA 18a.
developed. On the basis of the title reaction, we de- sidering the large number of commercially available
veloped a two-step method to produce this compound aldehydes and 1,3-dicarbonyls, we recommend this
by using commercially available precursors. The first method as a good choice for furan synthesis. The pro-
step involves an AlCl3-catalyzed reaction of octanal posed strategy integrating NBS as an oxidant in an
15a and ethyl 3-oxodecanoate 16a in the presence of acid-driven system of auto-tandem catalysis may also
NBS and thus produces 17a with 91% yield. The fol- be applied to establish other synthetic methodologies
lowing hydrolysis of 17a can produce 18a (Scheme 6). to heterocycles. This strategy is currently being inves-
This method can synthesize 18a with an overall yield tigated by our team.
of 79.2%.
In summary, polysubstituted furans were synthe-
sized from aldehydes and 1,3-dicarbonyls by using an
acid as a catalyst and NBS as an oxidant. This method
Experimental Section
is characterized by a simple operation, readily avail-
able reagents, and good synthetic efficiency. This
method also involves an auto-tandem catalysis based
General Procedure for the Reaction of Aldehydes,
1,3-Dicarbonyl Compounds and NBS
on a domino acid-acid-catalyzed reaction that played
a key role in the successful synthesis of furans. Con- equipped with triangle magnetic stirring. In a typical reac-
The reactions were conducted in a 10-mL V-type flask
Adv. Synth. Catal. 0000, 000, 0 – 0
6
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
tion, 1a (0.60 mmol) was mixed with 2a (0.50 mmol), NBS
(0.50 mmol) and AlCl3 (5 mol%) in acetonitrile (1.0 mL).
The mixture was then stirred at 808C for 4 h. After reaction,
the product was isolated by preparative TLC [eluting solu-
tion: petroleum ether/ethyl acetate=20/1 (v/v)]. Tests for
substrate scope were all performed with an analogous proce-
dure.
f) A. V. Gulevich, A. S. Dudnik, N. Chernyak, V. Ge-
vorgyan, Chem. Rev. 2013, 113, 3084–3213; g) C. Liu, L.
Zhou, D. Jiang, Y. Gu, Asian J. Org. Chem. 2016, 5,
367–372; h) S. R. Mothe, P. Kothandaraman, W. Rao,
P. W. H. Chan, J. Org. Chem. 2011, 76, 2521–2531.
[10] a) F. Stauffer, R. Neier, Org. Lett. 2000, 2, 3535–3537;
b) T. Aoyama, T. Nagaoka, T. Takido, M. Kodomari,
Synthesis 2011, 619–625; c) S. J. Ahmadi, S. Sadjadi, M.
Hosseinpour, M. Outokesh, R. Hekmatshoar, Catal.
Commun. 2009, 10, 1423–1426; d) B. C. Ranu, L. Adak,
S. Banerjee, Tetrahedron Lett. 2008, 49, 4613–4617;
e) W.-Y. Huang, Y.-C. Chen, K. Chen, Chem. Asian J.
2012, 7, 688–691.
[11] a) Y. Pan, S. Zhao, W. Ji, Z. Zhan, J. Comb. Chem.
2009, 11, 103–109; b) X. F. Z. Tan, D. Chen, Y. Shen,
C. C. Guo, J. Xiang, C. Zhu, Tetrahedron Lett. 2008, 49,
4110–4115; c) W. Ji, Y. Pan, S. Zhao, Z. Zhan, Synlett
2008, 3046–3052; d) C. R. Reddy, J. Vijaykumar, R.
Grꢁe, Synthesis 2010, 3715–3723; e) R. Sanz, D. Miguel,
A. Martꢃnez, J. M. ꢄlvarez-Gutiꢁrrez, F. Rodrꢃguez,
Org. Lett. 2007, 9, 727–730; f) P. N. Chatterjee, S. Roy,
Tetrahedron 2011, 67, 4569–4577; g) V. Cadierno, J.
Gimeno, N. Nebra, Adv. Synth. Catal. 2007, 349, 382–
394; h) C.-R. Liu, M.-B. Li, C.-F. Yang, S.-K. Tian,
Chem. Eur. J. 2009, 15, 793–797.
Acknowledgements
The authors thank the National Natural Science Foundation
of China (21373093) and the Fundamental Research Funds
for the Central Universities of China (2016YXZD033) for the
financial support. The Cooperative Innovation Center of
Hubei Province is also acknowledged.
References
[1] a) N. Shindoh, Y. Takemoto, K. Takasu, Chem. Eur. J.
2009, 15, 12168–12179; b) B.-L. Lu, L. Dai, M. Shi,
Chem. Soc. Rev. 2012, 41, 3318–3339; c) J. E. Camp,
Eur. J. Org. Chem. 2017, 18, 425–433.
[12] a) Y. R. Lee, M. W. Byun, B. S. Kim, Bull. Korean
Chem. Soc. 1998, 19, 1080–1083; b) S. Tang, K. Liu, Y.
Long, X. Qi, Y. Lan, A. Lei, Chem. Commun. 2015, 51,
8769–8772; c) J. Daru, Z. Benda, A. Poti, Z. Novak, A.
Stirling, Chem. Eur. J. 2014, 20, 15395–15400; d) I. I.
Roslan, J. Sun, G.-K. Chuah, S. Jaenicke, Adv. Synth.
Catal. 2015, 357, 719–726; e) C. He, S. Guo, J. Ke, J.
Hao, H. Xu, H. Chen, A. Lei, J. Am. Chem. Soc. 2012,
134, 5766–5769; f) A. Sivan, A. Deepthi, V. Nandialath,
Synthesis 2011, 2466–2470; g) A. Arcadi, G. Cerichelli,
M. Chiarini, S. D. Giuseppe, F. Marinelli, Tetrahedron
Lett. 2000, 41, 9195–9198; h) Y. Ma, S. Zhang, S. Yang,
F. Song, J. You, Angew. Chem. 2014, 126, 8004–8008;
Angew. Chem. Int. Ed. 2014, 53, 7870–7874.
[13] a) M. Zheng, L. Huang, W. Wu, H. Jiang, Org. Lett.
2013, 15, 1838–1841; b) X. Zhang, W. Dai, W. Wu, S.
Cao, Org. Lett. 2015, 17, 2708–2711; c) L. Xu, X.
Huang, F. Zhong, Org. Lett. 2006, 8, 5061–5064; d) C.-
Y. Zhou, P. W. H. Chan, C.-M. Che, Org. Lett. 2006, 8,
325–328.
[2] D. E. Fogg, E. N. dos Santos, Coord. Chem. Rev. 2004,
248, 2365–2379.
[3] I. Saikia, A. J. Borah, P. Phukan, Chem. Rev. 2016, 116,
6837–7042.
[4] Dor reviews on the implementation of bromination re-
actions with NBS, see: a) R. H. Vekariya, H. D. Patel,
Tetrahedron 2014, 70, 3949–3961; b) H. Veisi, R. Ghor-
bani-Vaghei, Tetrahedron 2010, 66, 7445–7463.
[5] a) X. L. Hou, Z. Yang, H. N. C. Wong, Prog. Hetero-
cycl. Chem. 2003, 15, 167–205; b) B. A. Keay, P. W.
Dibble, Comprehensive Heterocyclic Chemistry II,
(Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven),
Elsevier, Oxford, U. K, 1997; Vol. 2, pp 395–436.
[6] a) M. J. Palframan, G. Pattenden, Chem. Commun.
2014, 50, 7223–7242; b) H. Li, Q. Zhang, P. S. Bhadury,
S. Yang, Curr. Org. Chem. 2014, 18, 547–597.
[7] a) O. Gidron, L. J. W. Shimon, G. Leitus, M. Bendikov,
Org. Lett. 2012, 14, 502–505; b) O. Gidron, A. Dad-
vand, Y. Sheynin, M. Bendikov, D. F. Perepichka,
Chem. Commun. 2011, 47, 1976–1978; c) U. H. F. Bunz,
Angew. Chem. 2010, 122, 5159–5162; Angew. Chem.
Int. Ed. 2010, 49, 5037–5040; d) O. Gidron, Y. Diskin-
Posner, M. Bendikov, J. Am. Chem. Soc. 2010, 132,
2148–2150.
[14] R. Yan, J. Huang, J. Luo, P. Wen, G. Huang, Y. Liang,
Synlett 2010, 1071–1074.
[15] K. Komeyama, Y. Ohama, K. Takaki, Chem. Lett. 2011,
40, 1103–1104.
[16] R. Ballini, S. Gabrielli, A. Palmieri, Synlett 2010, 2468–
2470.
[17] Y. Yue, Y. Zhang, W. Song, X. Zhang, J. Liu, K. Zhuo,
Adv. Synth. Catal. 2014, 356, 2459–2464.
[8] a) B. H. Lipshutz, Chem. Rev. 1986, 86, 795–819; b) P.
Merino, T. Tejero, J. I. Delsoa, R. Matuteb, Curr. Org.
Chem. 2007, 11, 1076–1119.
[9] For general reviews on furan synthesis, see: a) X. L.
Hou, H. Y. Cheng, T. Y. Hon, P. L. Kwan, T. H. Lo,
D. Y. Tong, H. N. C. Wong, Tetrahedron 1998, 54, 1955–
2020; b) B. Konig, Science of Synthesis: Houben-Weyl
Methods of Molecular Transformations, (Ed.: G. Maas),
Georg Thieme Verlag, Stuttgart, Germany 2000, Vol. 9,
p 183; c) R. C. D. Brown, Angew. Chem. 2005, 117,
872–874; Angew. Chem. Int. Ed. 2005, 44, 850–852;
d) S. F. Kirsch, Org. Biomol. Chem. 2006, 4, 2076–2080;
e) N. T. Patil, Y. Yamamoto, ARKIVOC 2007, 121–141;
[18] J. Bao, J. Ren, Z. Wang, Eur. J. Org. Chem. 2012, 2511–
2515.
[19] a) A. Padwa, D. J. Austin, M. Ishida, C. L. Muller, S. S.
Murphree, P. E. Yeske, J. Org. Chem. 1992, 57, 1161–
1169; b) A. Padwa, S. S. Murphree, P. E. Yeske, J. Org.
Chem. 1990, 55, 4241–4242; c) D. Schmidt, C. C. Mala-
kar, U. Beifuss, Org. Lett. 2014, 16, 4862–4865.
[20] C. R. Reddy, M. D. Reddy, J. Org. Chem. 2014, 79,
106–116.
Adv. Synth. Catal. 0000, 000, 0 – 0
7
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
asc.wiley-vch.de
[21] S. R. Mothe, S. J. L. Lauw, P. Kothandaraman, P. W. H.
Chan, J. Org. Chem. 2012, 77, 6937–6947.
[28] Bromination with NBS is known to be catalyzed by
many acid catalysts. For some examples, see: a) V. L.
Heasley, K. E. Wade, T. G. Aucoin, D. E. Gipe, D. F.
Shellhamer, J. Org. Chem. 1983, 48, 1377–1379;
b) G. K. S. Prakash, T. Mathew, D. Hoole, P. M. Es-
teves, Q. Wang, G. Rasul, G. A. Olah, J. Am. Chem.
Soc. 2004, 126, 15770–15776; c) K. Shibatomi, Y.
Zhang, H. Yamamoto, Chem. Asian. J. 2008, 3, 1581–
1584.
[29] For a recent review, see: a) P. Ravichandiran, B. Lai, Y.
Gu, Chem. Rec. 2017, 17, 142–183; for see some select-
ed examples, see: b) H. Amri, M. Rambaud, J. Villieras,
Tetrahedron 1990, 46, 3535–3546; c) H. C. Brown,
J. V. N. V. Prasad, S. H. Zee, J. Org. Chem. 1985, 50,
1582–1589; d) M. C. Pirrung, J. Zhang, K. Lackey, D. D.
Sternbach, F. Brown, J. Org. Chem. 1995, 60, 2112–
2124.
[30] a) K. Snegaroff, S. Komagawa, F. Chevallier, P. C. Gros,
S. Golhen, T. Roisnel, M. Uchiyama, F. Mongin, Chem.
Eur. J. 2010, 16, 8191–8201; b) J. D. Ripoll, A. Serna, D.
Guerra, A. Restrepo, J. Phy. Chem. A. 2010, 114,
10917–10921.
[31] a) A. Gandini, A. J. D. Silvstre, C. P. Neto, A. F. Sousa,
M. Gomes, Polym. Chem. 2009, 47, 295–298; b) M.
Gomes, A. Gandini, A. J. D. Silvestre, Polym Chem.
2011, 49, 3759–3768.
[22] a) P. Li, J. Zhao, C. Xia, W. Li, Org. Lett. 2014, 16,
5992–5995; b) Y. Jiang, V. Z. Y. Khong, E. Lourdusamy,
C. M. Park, Chem. Commun. 2012, 48, 3133–3135;
c) H. Hagiwara, K. Sato, D. Nishino, T. Hoshi, T.
Suzuki, M. Ando, J. Chem. Soc. Perkin Trans. 1 2001,
2946–2957; d) L. Xia, Y. R. Lee, Eur. J. Org. Chem.
2014, 3430–3442; e) J. S. Clark, A. Boyer, A. Aimon,
P. E. Garcia, D. M. Lindsay, A. D. F. Symington, Y.
Danoy, Angew. Chem. 2012, 124, 12294–12297; Angew.
Chem. Int. Ed. 2012, 51, 12128–12131; f) J. S. Clark, F.
Romiti, K. F. Hogg, M. H. S. A. Hamid, S. C. Richter,
A. Boyer, J. C. Redman, L. J. Farrugia, Angew. Chem.
2015, 127, 5836–5839; Angew. Chem. Int. Ed. 2015, 54,
5744–5747; g) J. Gonzꢅlez, J. Gonzꢅlez, C. Pꢁrez-Calle-
ja, L. A. Lꢆpez, R. Vicente, Angew. Chem. 2013, 125,
5965–5969; Angew. Chem. Int. Ed. 2013, 52, 5853–5857.
[23] a) H. Pellissier, Tetrahedron 2014, 70, 4991–5031; b) C.
Liu, L. Zhou, W. Huang, M. Wang, Y. Gu, Tetrahedron
2016, 72, 563–570.
[24] Y. Banno, R. Hara, R. Tokunoh, PCT Int. Appl. 2009,
WO 2009057784 A1.
[25] D. Zhao, B. Sun, J. Ren, F. Li, S. Song, X. Lv, C. Hao,
M. Cheng, Bioorg. Med. Chem. 2015, 23, 1356–1365.
[26] a) W. S. Trahanovsky, C.-H. Chou, T. J. Cassady, J. Org.
Chem. 1994, 59, 2613–2615; b) M. L. Hossain, F. Ye, Y.
Zhang, J. Wang, Tetrahedron 2014, 70, 6957–6962; c) T.
Aoyama, T. Nagaoka, T. Takido, M. Kodomaric, Syn-
thesis 2011, 619–625.
[32] a) Y. Xu, J.-J. Zhong, Bioresource Technol. 2011, 102,
9167–9174; b) X.-Y. Wang, Y.-Q. Xu, S.-J. Lin, Z.-Z.
Liu, J.-J. Zhong, Appl. Environ. Microb. 2011, 77,
6253–6257.
[27] R. A. Kretchmer, R. A. Laitar, J. Org. Chem. 1978, 43,
4596-4598.
Adv. Synth. Catal. 0000, 000, 0 – 0
8
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!

COMMUNICATIONS
Auto-Tandem Catalysis-Induced Synthesis of Trisubstituted
Furans through Domino Acid-Acid-Catalyzed Reaction of
Aliphatic Aldehydes and 1,3-Dicarbonyl Compounds by
using N-Bromosuccinimide as Oxidant
9
Adv. Synth. Catal. 2017, 359, 1 – 9
Wenbo Huang, Changhui Liu,* Yanlong Gu*
Adv. Synth. Catal. 0000, 000, 0 – 0
9
ꢂ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!