A coupling reaction of aryltributyltin with olefins mediated by palladium(II) acetate

Article abstract of DOI:10.1055/s-1999-2562

Phenytributyltin is found to react with butyl acrylate in the presence of Pd(OAc)₂ (10 mol%), Cu(OAc)₂ (3 mol), and LiOAc (2 mol) in DMF to afford butyl 3-phenylpropenoate in 77% yield. Methyl vinyl ketone, acrolein, acrylonitrile, and styrene are also applicable to this reaction as a substrate.

Full text of DOI:10.1055/s-1999-2562

LETTER
99
A Coupling Reaction of Aryltributyltin with Olefins Mediated by
Palladium(II) Acetate
Kazunori Hirabayashi, Jun-ichi Ando, Yasushi Nishihara, Atsunori Mori,* and Tamejiro Hiyama#
Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta, Yokohama 226-8503, Japan
Fax 81-45-924-5224; E-mail: amori@res.titech.ac.jp
Received 16 October 1998
Abstract: Phenytributyltin is found to react with butyl acrylate in
the presence of Pd(OAc) (10 mol%), Cu(OAc) (3 mol), and LiO-
2
2
Ac (2 mol) in DMF to afford butyl 3-phenylpropenoate in 77%
yield. Methyl vinyl ketone, acrolein, acrylonitrile, and styrene are
also applicable to this reaction as a substrate.
Key words: Mizoroki-Heck type, aryltin, palladium(II) acetate,
copper(II) acetate, lithium acetate
Scheme 1
tuted phenyltributyltins also effected the reactions. How-
ever, alkenyl- and alkynyltributyltin compounds
underwent a homo-coupling to afford conjugated dienes
and diynes, respectively. Tetrabutyltin could not transfer
a butyl group to acrylate 2a.
The Mizoroki-Heck (M-H) reaction serves as one of the
significant methods for carbon-carbon bond formation at
2
an sp carbon starting with an organic halide and an ole-
1
fin. Although, the use of organometallic or -metalloid re-
agents instead of the organic halides is also a method of
2
choice, such reactions have not well been studied. The It is remarkable that the reaction of aryltin compounds
M-H type reaction with organotin compounds in the pres- proceeded cleanly compared with that of silanols to afford
ence of a stoichiometric amount of palladium(II) was doc- the corresponding products along with a small amount of
umented in 1969 by Heck, the reactivity of the tin reagent the homo-coupled biaryls and none of unidentified
was reported therein to be inferior to organomercury re- byproducts. However, prolonged exposure of the aryl-
agents. The reactions of organotin reagents to an olefinic tributyltin to the palladium catalyst was found to enhance
compound have little been studied thereafter, in contrast the yield of the undesired homo-coupled product, which,
2
e
3
with numerous studies for the Migita-Stille coupling, one in contrast, was rarely observed in the coupling reaction of
4
of the most practical cross-coupling reactions.
silanols under the similar conditions. Indeed, when 10 was
stirred at room temperature for 5 min with 10 mol% of
Pd(OAc) , Cu(OAc) , and LiOAc prior to the addition of
On the other hand, we recently disclosed that the reaction
of aryl- and alkenylsilanols, a typical example of the met-
alloid reagent, with several olefins afforded the identical
product with M-H reaction in the presence of Cu(II) salt
and a catalytic amount of palladium(II) acetate. These
findings prompted us to investigate a possibility of such
2
2
2
a, the yield of biaryl was increased to 72% and the yield
5
of 11 was decreased to 8% (see entry 10 of Table 1: the
result for the immediate addition of 2a to the reaction sys-
tem).
reactions with organotin compounds. We herewith wish to We understand the reaction mechanism in terms of the
describe that organotin compounds are also an appropriate following 3 steps: (i) transmetalation of an aryl group
organometalloid reagent to effect the palladium catalyzed from tin to Pd(II), (ii) insertion of a terminal olefin to a
Mizoroki-Heck type coupling reaction with olefins.
Pd(II)-carbon bond, (iii) a b-hydride elimination to give
the corresponding product and Pd(0), which is oxidized to
Pd(II) by a Cu(II) salt as was the case of the Wacker pro-
When the reaction was carried out with phenytributyltin
(1, 1 mmol) with butyl acrylate (2a, 1 mmol) under the
7
cess. Indeed, in the absence of copper(II) acetate, the re-
conditions for silanols [Pd(OAc) (10 mol%), Cu(OAc)2
2
action of Scheme 1 using Pd(OAc) (20 mol% or 100
2
(
3 mmol), and LiOAc (2 mmol) in DMF, 100 °C, 24 h],
mol%) in DMF at 100 °C for 3 days gave 3a in 8 or 60%
yield, respectively.
butyl 3-phenylpropenoate (3a) was obtained in 77% yield
along with biphenyl (16% yield), a homo-coupled product
6
of 1.
An alternative mechanism was suggested for the similar
reaction using an organoboronic acid by Cho and Uemu-
Organotin compound 1 was also found to react with elec-
tron-deficient terminal olefins such as acrylates, acryloni-
trile, methyl vinyl ketone and acrolein to give the M-H
products in good yields as summarized in Table 1. Styrene
also underwent the reaction to give trans-stilbene in 73%
yield. An electron-rich olefin like butyl vinyl ether turned
out to be much less reactive. In addition, variously substi-
2c
ra, who described that the initial step of the catalytic cy-
cle is an oxidative addition of Pd(0) to the carbon-boron
bond. Since an organotin reagent, in general, is shown to
exhibit divergent characters toward the reactions of palla-
8
dium species, the oxidative addition to Pd(0) and the
9
transmetalation with Pd(II), the reaction pathway involv-
Synlett 1999, No. 1, 99–101 ISSN 0936-5214 © Thieme Stuttgart · New Yorkrk

1
00
K. Hirabayashi et al.
LETTER
ing the oxidative addition might also be possible. Howev-
er, treatment of 1 with 2a in the presence of a Pd(OAc)2
catalyst in AcOH/AcONa, the similar conditions of Cho
and Uemura, gave no trace of 3a. Thus, the mechanism in-
volving the oxidative addition is unlikely in the reaction
of the aryltin reagent.
The transmetalation mechanism illustrated in Fig 1 sug-
gests that Bu SnOAc (12) should be produced along with
3
1
a Ph-Pd species from 1 and Pd(OAc) . Indeed, H and
2
1
19
Sn NMR spectra of a reaction mixture in DMF-d
7
1
119
showed signals at 1.93 ppm ( H) and 7.7 ppm ( Sn), re-
spectively, both ascribed to 12 in AcOH.10
In summary, aryltributyltins are found to undergo the M-
H type reaction with a variety of olefins as observed with
arylsilanols, arylboronic acids, and aryl halides. In partic-
ular, the reaction of tin reagents was suggested to proceed
through a transmetalation in a manner similar to silanols
but in contrast to boronic acids or aryl halides.
General procedure for the coupling reaction of aryltin re-
agent with olefin: To a solution of Pd(OAc) (0.03 mmol),
2
Cu(OAc) (0.9 mmol) and LiOAc (0.6 mmol) in DMF (2
2
mL) placed in a screw capped sealed glass tube were add-
ed successively butyl acrylate 2a (0.32 mmol) and phenyl-
tributyltin 1a (0.3 mmol) at room temperature under
argon. The mixture was heated with stirring at 100 °C for
2
4 h and then, after cooling, passed through a Celite pad
with diethyl ether (30 mL) as an eluent. The eluate was
washed with 1 M HCl aq. (15 mL), sat. NaHCO aq. (2 x
3
1
5 mL), 5% NH aq. (3 x 100 mL), and brine (20 mL). The
3
ethereal solution was dried over MgSO and concentrated
4
under reduced pressure to leave a crude oil, which was pu-
rified by flash column chromatography on silica gel (hex-
anes/AcOEt = 10/1) to give 3a in 77% yield.
Acknowledgement
We are indebted to Professor Masanori Kosugi and Dr. Keigo Fug-
ami of Gunma University for helpful discussion.
Synlett 1999, No. 1, 99–101 ISSN 0936-5214 © Thieme Stuttgart · New York

LETTER
A Coupling Reaction of Aryltributyltin with Olefins Mediated by Palladium(II) Acetate
101
References and Notes
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#
Present address: Department of Material Chemistry, Graduate
School of Engineering, Kyoto University, Yoshida, Kyoto
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Synlett 1999, No. 1, 99–101 ISSN 0936-5214 © Thieme Stuttgart · New York