Efficient synthesis of 3-arylbutadiene sulfones using the Heck–Matsuda reaction

Article abstract of DOI:10.1016/j.mencom.2021.07.037

An efficient and practical method for a scalable synthesis of 3-arylbutadiene sulfones deals with the ligand-free Heck–Matsuda reaction of sulfolene with aryldiazonium tetrafluoroborates followed by triethylamine-promoted double bond shift.

Full text of DOI:10.1016/j.mencom.2021.07.037

Mendeleev
Communications
Mendeleev Commun., 2021, 31, 548–549
Efficient synthesis of 3-arylbutadiene sulfones
using the Heck–Matsuda reaction
Sergey A. Rzhevskiy, Vasilii N. Bogachev, Lidiya I. Minaeva, Grigorii K. Sterligov,
Mikhail S. Nechaev, Maxim A. Topchiy and Andrey F. Asachenko*
A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences,
119991 Moscow, Russian Federation. E-mail: aasachenko@ips.ac.ru
DOI: 10.1016/j.mencom.2021.07.037
Ar
An efficient and practical method for a scalable synthesis of
3-arylbutadiene sulfones deals with the ligand-free Heck–
Matsuda reaction of sulfolene with aryldiazonium tetra-
fluoroborates followed by triethylamine-promoted double
bond shift.
1ꢃ PdꢄOAcꢃ2 ꢄꢅ molꢆꢃ
MeOꢇ or ꢈꢇꢁꢉ ꢊ0 ꢋCꢉ 1 h
−
ArN2ꢀBꢁꢂ
ꢀ
S
2ꢃ EtꢅNꢉ Cꢇ2Cl2
refluꢌꢉ ꢍ−2ꢂ h
S
O
O
O
O
1ꢍ eꢌamꢎles
Keywords: arylation, cross-coupling, Pd-catalysis, butadiene, sulfolene, aryldiazonium salts.
3-Sulfolenes1 are valuable key intermediates widely used in the
synthesis of sulfolanes,2 polycyclic heterocycles1(b),3 and
conjugated unsaturated compounds4 as well as in natural product
synthesis.5 3-Sulfolenes are usually considered as ‘protected
dienes’where the electron-withdrawing properties of the sulfone
group are responsible for the easy C2 and C5 deprotonation,
along with the double bond shift, depending on reaction
conditions. The alkylation at C2 with C3-substituted compounds
readily occurs, except for cases when the carbanion is stabilized
with a silyl or phenyl group.6 Extrusion of SO2 may be further
easily carried out,4(b),4(f),7 therefore sulfolenes are very beneficial
in the syntheses of terpenes, for example (E)-ocimene7(a)
obtained from 2-methylsulfolene, the commercially available
isoprene adduct of SO2. Although 3-sulfolene applications are
very rewarding, it is all the more surprising that the synthesis of
3-arylbutadiene sulfones is documented scarcely.
sulfones. Based on the abovementioned data,12 we started our
search for optimal conditions of the process (see Scheme 1 and
Online Supplementary Materials, Table S1, entries 1-13).
+
We used PhN2 BF4- as a model substrate, Pd2(dba)3 ∙ CHCl3
and Pd(OAc)2 as a palladium source and examined various
solvents. The highest yield of 95% was achieved in case of
Pd(OAc)2 and Pd2(dba)3 ∙ CHCl3 at 50°C in methanol. Decrease
in temperature to the ambient one leads to a moderate decrease
in the yield of product 1. It should be noted that intermediate 1
+
(see Scheme 1) was isolated only for PhN2 BF4- as a substrate,
in case of all other aryldiazonium salts we performed one-pot
process giving the target 3-sulfolenes of type 2 without the
intermediate isolation.
We investigated the activity of the found catalytic system
suitable for a variety of substrates (Scheme 2). Substrates, bearing
various electron-donating and withdrawing groups at ortho-,
meta- and para-positions along with the sterically hindered
substituents, were systematically tested. Aryldiazonium salts
containing electron-donating and electroneutral substituents
react with 3-sulfolene under modified conditions in methanol to
afford 3-arylbutadiene sulfones 2a-e with the good to excellent
yields (see Scheme 2). Also, aryldiazonium salts with such
electron-withdrawing groups as Cl (2f,h), Br (2g) and CF3 (2i)
give the yields from 77 to 92% in methanol.
However, our attempt to introduce other electron-withdrawing
(for products 2j-l) or sterically hindered (for products 2m-p)
substituents into aryldiazonium salts caused serious drop in the
cross-coupling yields up to 0%. Consequently, we continued
search for optimal conditions for these substrates. We used
Among the described methods for the synthesis of 3-aryl-
butadiene sulfones, SO2 addition to these dienes is not easy.8
The alternative transformation of 3-bromobutadiene sulfones
requires the application of poorly accessible alkylcuprates9
under inert atmosphere, whereas the Stille reaction10 of exotic
3-stannylated butadiene is not environmental friendly.
The Heck reaction resulting in 3-arylbutadiene sulfones as the
products seems to be the most convenient and promising. The
Heck reaction was earlier developed2(d),11 on the narrow starting
material scope, using expensive aryl iodides along with high
loadings of Pd-catalyst (5 mol%). Since aryl halides in Heck
reaction can be replaced with cheap and readily accessible aryl-
diazonium salts, we reasoned for improvement of the efficiency
using the scalable Heck-Matsuda reaction. In general, the
Heck-Matsuda reaction with aryldiazonium salts results in
3-aryl-4-sulfolenes of type 1 which can be quantitatively
isomerized into desired 3-arylbutadiene sulfones (Scheme 1).
The only paper describing this approach12 contains only six
examples while steric and electronic effects of the substituents
are not studied. In continuous search for efficient catalysts13 for
modern synthetic methods,14 we report herein on the Heck-
Matsuda reaction for the convenient synthesis of 3-arylbutadiene
Ph
Ph
i
ii
−
PhN2ꢀBꢁꢂ
ꢀ
S
ꢃꢄꢅ
ꢆ100ꢅ
S
S
O
O
O
O
O
O
ꢁ
ꢀa
Scheme 1 Reagents and conditions: i, Pd(OAc)2 (3 mol%), MeOH
(2 ml mmol-1), 50°C, 1 h; ii, CH2Cl2 (5 ml mmol-1), Et3N (1 ml mmol-1),
reflux, 24 h.
© 2021 Mendeleev Communications. Published by ELSEVIER B.V.
on behalf of the N. D. Zelinsky Institute of Organic Chemistry of the
Russian Academy of Sciences.
– 548 –

Mendeleev Commun., 2021, 31, 548–549
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Scheme 2 Reagents and conditions: i, Pd(OAc)2 (3 mol%), MeOH
(2 ml mmol-1), 50°C, 1 h; ii, Pd(OAc)2 (3 mol%), THF (5 ml mmol-1),
50°C, 1 or 4 h; iii, Et3N (1 ml mmol-1), CH2Cl2 (5 ml mmol-1), reflux,
6-24 h.
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+
-
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13-17) and found that the yields from good to almost quantitative
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Pd(OAc)2 and THF as the solvent (see Scheme 2). Carrying out
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salts with weak electron-withdrawing substituents (see Scheme 2,
products 2f-i). On the contrary, for substrates with electron-
donating and electroneutral groupings the yields stayed better in
methanol (products 2a-e).
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In conclusion, we have developed a simple and efficient
method for the preparation of 3-arylbutadiene sulfones via the
Heck-Matsuda reaction. The reactions can be carried out in a
gram scale, using a bench stable and inexpensive aryldiazonium
salts in methanol or THF in the presence of Pd(OAc)2 under
ligand-free conditions. In view of the readily available starting
materials, simple operation of the process, as well as high
regioselectivity, this methodology may become a useful tool for
the synthesis of branched 3-arylbutadiene sulfones and their
derivatives. The new method is expected to find applications in
medicinal chemistry and organic synthesis.
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Maxim A. Topchiy, Vasilii N. Bogachev, Grigorii K. Sterligov
and Andrey F. Asachenko are thankful to Russian Science
Foundation (RSF) for financial support (project no.
19-73-10185). Part of this work was carried out by
Sergey A. Rzhevskiy, Lidiya I. Minaeva and Mikhail S. Nechaev
as part of the A. V. Topchiev Institute of Petrochemical Synthesis
(TIPS) Russian Academy of Sciences (RAS) State Program.
This work was performed using the equipment of the Shared
Research Center ‘Analytical center of deep oil processing and
petrochemistry of TIPS RAS’.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2021.07.037.
Received: 19th March 2021; Com. 21/6496
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