HUSY zeolite promoted hydrophenylation of alkynes conjugated with electron-withdrawing substituents

Article abstract of DOI:10.1016/j.mencom.2016.11.013

Arylacetylenes, conjugated with electron-withdrawing groups, ArC[tbnd6]C(EWG) [EWG = SO₂Ph, PO(OEt)₂, COMe, CO₂Me] in reaction with benzene at room temperature or 130?°C (glass high pressure tube) for 1–10?h under the acti

Full text of DOI:10.1016/j.mencom.2016.11.013

Mendeleev
Communications
Mendeleev Commun., 2016, 26, 500–501
HUSY zeolite promoted hydrophenylation of alkynes
conjugated with electron-withdrawing substituents
Dmitry S. Ryabukhina,b and Aleksander V. Vasilyev*a,b
a Department of Organic Chemistry, Institute of Chemistry, St. Petersburg State University,
199034 St. Petersburg, Russian Federation. Fax: +7 812 670 9390; e-mail: aleksvasil@mail.ru
b Department of Chemistry, St. Petersburg State Forest Technical University, 194021 St. Petersburg,
Russian Federation
DOI: 10.1016/j.mencom.2016.11.013
Arylacetylenes, conjugated with electron-withdrawing groups,
zeolite H+
R
ArCºC(EWG) [EWG = SO2Ph, PO(OEt)2, COMe, CO2Me]
in reaction with benzene at room temperature or 130°C (glass
high pressure tube) for 1–10 h under the action of acidic
zeolite HUSY (Si/Al ratio is 15) afford products of hydro-
phenylation of acetylene bond Ar(Ph)C=CH(EWG) in yields
of 56–98%.
(CBV-720)
+
EWG
EWG
20–130 °C,
1–10 h
high pressure
R
Ph
E,Z
56–98%
R = H, Alk, Hal
EWG = COMe, CO2Me, SO2Ph, PO(OEt)2
Acidic zeolites considered as ‘green’ catalysts are widely used
in organic synthesis.1–6 Reported uses include Friedel–Crafts
acylation, alkylation and alkenylation reactions,7–10 ionic hydro-
genation,11 and the synthesis of different carbo-8,12–14 and hetero-
cycles.10 Zeolites can be also modified by metals, for instance
Cui,15–21 that opens new opportunities in acetylene chemistry
for the preparation of triazoles,15–17 diynes,18,19 or propargyl-
amines.20
We undertook this research based on our works on electro-
philic activation of alkynes in Brønsted superacids22 and our
recent study on zeolite-promoted cyclization of N-aryl amides
of acetylene carboxylic acids into quinolinone derivatives,23 and
superacidic transformations of lignin.24 The main goal of this
work was a study of reactions of alkynes, bearing electron-with-
drawing groups, with arenes under the action of acidic zeolite
HUSY, which is commercially available as zeolite CBV-720.
Acetylenes RCºC(EWG) 1, conjugated with strong electron-
withdrawing groups, may be electrophilically activated only
in Brønsted superacids (CF3SO3H, FSO3H)22 or strong Lewis
acids (AlCl3, AlBr3).25 Thus, protonation of such acetylene subs-
trates in Brønsted superacids gives highly reactive dications
RC+=CH(EWG–H)+, which may further react with arenes to
form products of hydroarylation of triple bond.
Table 1 Reactions of alkynes 1a–g with benzene under the action of acidic
zeolite HUSY, leading to alkenes E,Z-2a–g.a
Starting
alkyne
Product
(E/Z ratio)
Entry
Ar
EWG
T/°C t/h
Yield (%)
1
2
1a
1b
1b
1c
1c
1d
1d
1e
1e
1f
Ph
Ph
Ph
Ph
Ph
SO2Ph
130 3 2a
98
14b
PO(OEt)2 130 1 2b
PO(OEt)2 130 10 2b
3
56
14b
4
COMe
COMe
~20 10 2c
130 1 2c
5
oligomers
6
2-MeC6H4 COMe
2-MeC6H4 COMe
130 1 E/Z-2d (0.1:1) 37
~20 2 E/Z-2d (0.1:1) 98
7
8
Ph
Ph
CO2Me ~20 10 2e
CO2Me 130 1 2e
5b
9
98
10
11
4-ClC6H4 CO2Me 130 1 E/Z-2f (0.8:1) 94
2-FC6H4 CO2Me 130 1 E/Z-2g (0.13:1) 82
1g
aA typical charge of reagents: zeolite (0.45 g), alkyne (0.2 mmol), benzene
(5 ml); the ratio of alkyne:zeolite Brønsted acidic sites was ~2:1 (see
estimation of zeolite acidity in Online Supplementary Materials). bIncomplete
conversion of alkyne.
Ar
Ar
C
C
EWG + PhH
C
CH EWG
Ph
1a–g
E,Z-2a–g
Analogously to Brønsted superacid-promoted reactions, we
expected that zeolite HUSY would be capable of activating alkynes,
which bear electron-withdrawing substituents, in reaction with
benzene. Indeed, arylacetylenes 1a–g reacted with benzene under
the action of zeolite HUSY to produce alkenes 2a–g (Scheme 1,
Table 1). Experimental procedure is simple and involves heating
of alkyne 1a–g in excess of benzene with zeolite in glass high
pressure tube at 130°C for 1 h† to give hydrophenylation products
Scheme 1 Conditions: zeolite HUSY, high pressure tube, 130 or 20°C.
For Ar and EWG, see Table 1.
2a–g in 56–98% yields. Among other investigated substrates,
acetylene ketones 1c,d afforded the target compounds 2c,d,
respectively, at room temperature (entries 4, 7). However, at higher
temperature 130°C yields of these products were much lower
†
Zeolite CBV-720 (obtained from Zeolyst Int.) was activated at 550°C
trated in vacuo to provide a residue, which was subjected to chromato-
graphic separation on silica gel using hexane–ethyl acetate as an eluent.
Phenyl 2,2-diphenylethenyl sulfone 2a. Oily compound. 1H HMR
(500 MHz, CDCl3) d: 7.02 (s, 1H, =CH), 7.07 (d, 2Harom, J 7.4 Hz), 7.20
(d, 2Harom, J 8.0 Hz), 7.27–7.35 (m, 8Harom), 7.48 (t, 1Harom, J 7.4 Hz),
7.57 (d, 2Harom, J 8.0 Hz). MS, m/z (%): 320 M+ (35), 255 (5), 195 (8),
178 (100).
under air for 4 h. The activated zeolite (0.45 g), acetylene 1a–g (0.2 mmol)
and benzene (5 ml) were loaded in a 15 ml glass high pressure tube (ACE).
The resulting suspension was stirred magnetically at room temperature or
130°C for the time indicated in Table 1. After cooling, the reaction mixture
was filtered to remove the zeolite catalyst. The zeolite was subsequently
boiled with several portions of MeOH (3×10 ml) and filtered off each time.
The combined organic phases (benzene and methanol solutions) were concen-
For more details, see Online Supplementary Materials.
© 2016 Mendeleev Communications. Published by ELSEVIER B.V.
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
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Mendeleev Commun., 2016, 26, 500–501
5 C. H. Zhou, X. Xia, C. X. Lin, D. S. Tong and J. Beltramini, Chem. Soc.
as oligomeric materials were formed (entries 5, 6). Concerning
the stereoselectivity of the reaction, predominant formation of
Z-isomers, as syn-addition of proton and phenyl moiety to the
triple bond, was observed. Presumably, this syn-addition is more
energetically preferable in zeolite cage.
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The reaction mechanism may include electrophilic activation
of alkynes 1a–g by Brønsted and Lewis acid sites of the zeolite,
leading to dications (cf. refs. 22,25), which react with benzene.
Important that other arenes (toluene, o-, m-, p-xylenes) in the
zeolite promoted reaction with alkynes 1a–g gave oligomers.
These electron rich arenes may coordinate to the acidic sites
of zeolites, blocking them and directing compounds 1a–g into
other reaction pathways. On the other hand, these arenes, as very
reactive p-nucleophiles, may participate in several reactions with
cationic species derived from starting alkynes 1a–g. Apart from
that, electron deficient o-dichlorobenzene did not take part in this
reaction. One should search for reaction conditions (solvents,
concentration of reagent, temperature, etc.) to involve substituted
benzenes in this research.
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In conclusion, for the first time, we carried out intermolecular
hydrophenylation of acetylene bond of alkynes, conjugated with
electron-withdrawing groups, in reaction with benzene under the
action of acidic zeolite.
17 T. Boningari, A. Olmos, B. M. Reddy, J. Sommer and P. Pale, Eur. J.
Org. Chem., 2010, 6338.
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19 P. Kuhn, A. Alix, M. Kumarraja, B. Louis, P. Pale and J. Sommer, Eur.
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This study was supported by the Russian Science Foundation
(grant no. 14-13-00448).
20 M. K. Patil, M. Keller, B. M. Reddy, P. Pale and J. Sommer, Eur. J. Org.
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21 A. Alix, S. Chassaing, P. Pale and J. Sommer, Tetrahedron, 2008, 64,
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22 A. V. Vasilyev, Russ. Chem. Rev., 2013, 82, 187.
23 D. S. Ryabukhin and A.V. Vasilyev, Tetrahedron Lett., 2015, 56, 2200.
24 A.V. Kalugina, D. S. Ryabukhin, T. O.Artamonova, M.A. Khodorkovsky,
M. Ya. Zarubin and A.V. Vasilyev, Mendeleev Commun., 2014, 24, 353.
25 A. O. Shchukin, A. V. Vasilyev and E. V. Grinenko, Russ. J. Org. Chem.,
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Online Supplementary Materials
Supplementary data associated with this article (properties
of zeolite HUSY, 1H and 13C NMR spectra) can be found in the
online version at doi:10.1016/j.mencom.2016.11.013.
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Received: 31st March 2016; Com. 16/4893
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