A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction

Article abstract of DOI:10.1016/j.jorganchem.2009.03.030

Mono-, di-, tri- and tetra-functional organotin compounds were easily prepared in a sonicated Barbier reaction using ultrasound technology via coupling reaction of organo halides with tin halides (Bu₃SnCl, Bu₂SnCl₂, BuSnCl

Full text of DOI:10.1016/j.jorganchem.2009.03.030

Journal of Organometallic Chemistry 694 (2009) 2368–2374
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
A novel mode of access to polyfunctional organotin compounds
and their reactivity in Stille cross-coupling reaction
b,
Sandrine Lamandé-Langle a, Mohamed Abarbri b, Jérôme Thibonnet b, , Alain Duchêne
*
*
a Université de Nancy, Groupe SUCRES, UMR CNRS 7565, Faculté des Sciences, BP 239, Vandoeuvre Lès Nancy Cedex F-54506, France
b Laboratoire de Physicochimie des Matériaux et des Biomolécules, EA 4244, Faculté des Sciences de Tours, Parc de Grandmont, 37200 Tours, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Mono-, di-, tri- and tetra-functional organotin compounds were easily prepared in a sonicated Barbier
reaction using ultrasound technology via coupling reaction of organo halides with tin halides (Bu3SnCl,
Bu2SnCl2, BuSnCl3, SnCl4) mediated by magnesium metal. The di- and tri-functional organotin com-
pounds were tested in a Stille cross-coupling reaction in order to ascertain how many groups were
transferred.
Received 28 January 2009
Received in revised form 18 March 2009
Accepted 18 March 2009
Available online 26 March 2009
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Organotin compounds
Sonication
Pd cross-coupling
1. Introduction
methods in organic synthesis has been demonstrated by the many
reports in the literature on sonochemical reactions [6]. However
The considerable advances in the use of organotin compounds
as reagents or intermediates in organic synthesis in recent years
have prompted the preparation of many new organotin
compounds and the development of new rapid and convenient
synthesis procedures [1]. The formation of a carbon–carbon bond
by organotin compounds (especially tributylstannyl compounds)
and electrophiles is of considerable interest. Palladium-catalysed
cross-coupling of organotin compounds with organic electrophiles
(Stille reaction) has emerged as one of the main methods for the
creation of new carbon–carbon bonds [2]. Organotin compounds
have been extensively accessed in organic synthesis and are typi-
cally prepared by the reaction of organometallic compound (RMgX,
few publications have reported the synthesis of mono-functional
tributyltin compounds [7] and none have reported the synthesis
of di-, tri- and tetra-functional organotin compounds with this
technology.
2. Results and discussion
2.1. Preparation of mono-, di-, tri- and tetra-functional organotin
compounds
We first tested a simplified and improved one-step synthesis of
organotin compounds by Barbier reaction between stannyl chlo-
rides, magnesium turnings and organic halides using ultrasound,
without the presence of dibromoethane or iodine, as previously
recommended for the synthesis of only mono-functional organotin
compounds [7] (Scheme 1).
A wide range of organotin compounds were subjected to this
procedure to produce quite high yields of the corresponding
products. A clean multi-substitution (double, triple or quadruple)
reaction was also possible with di-, tri- and tetrachlorotin deriva-
tives and yielded polyfunctional organotin products. The results
are presented in Table 1.
As can be seen, this methodology was able to accommodate a
variety of organic functional halides and the yield was generally
nearly quantitative, except in the case of tetra-functional tin com-
pounds (entries 22–23) where experimental conditions needed to
be optimized. In the case of aryl or benzyl halides a small amount
of the duplicated product was obtained, except for entries 11 and
Rli, RZnX, etc.) which will react with organotin halides (RnSnCl4ꢀn
)
or by reactions of stannylanions with organic halides [3]. Alkynyl-
tin compounds are typically prepared by condensation of 1-al-
kynes with R3SnNR02 or R3SnOR0 and also by trapping of an
alkynyl metal with R3SnX [4]. These methods allow synthesis of
mono-, di-, tri- and tetra-functional organotin compounds, but in
particular mono-functional tributylorganotin compounds have
been synthesised with yields varying according to the nature of
the substituent. We were therefore interested to synthesise various
mono-, di-, tri- and tetra- functional organotin compounds by
sonication in order to improve yields and the methodology and
to create new organotin compounds according to our laboratory
experience [5]. The increased focus on the use of sonochemical
* Corresponding authors. Tel.: +33 247367359; fax: +33 247367073 (J. Thibonnet).
E-mail address: jerome.thibonnet@univ-tours.fr (J. Thibonnet).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.03.030

S. Lamandé-Langle et al. / Journal of Organometallic Chemistry 694 (2009) 2368–2374
2369
THF or Et2O
13. It should be noted that the quality of the reactants was not crit-
ical (solvent or halides), and they did not need careful purification
before use, and dibromoethane or iodine were not necessary to
start the reaction.
BunSnR4-n
BunSnCl4-n
+ Mg + RBr
))), rt
n = 3
n = 2
n = 1
n = 0
1 eq.
1 eq.
1 eq.
1 eq.
1.3 eq. 1.3 eq. reaction time: 15 min. to 2 h
1a-4a
1b-10b
1c-7c
1d-3d
3 eq.
4 eq.
5 eq.
3 eq.
4 eq.
5 eq.
reaction time: 1 to 2 h
reaction time: 1 h
reaction time: 2 h
2.2. Specific preparation of 1-alkynyltin compounds
R = alkyl, allyl, alkenyl, allenyl, aryl or heteroaryl
The preparation of 1-alkynyltin compounds with this method-
ology was not conclusive, and we therefore proceeded first with
Scheme 1.
Table 1
Preparation of mono-, di-, tri- and tetra-functional tin compounds.
Entry
n
R
Product
Yielda (%)
91
Literature yield (%)/(ref)
Commercial 95/[29]
No.
SnBu3
SnBu3
SnBu3
1
3
Allyl
1a
2
3
3
3
Vinyl
89
90
Commercial 85/[3b]
78/[11]
2a
3a
Isopropenyl
4
5
6
3
2
2
Allenyl
Methyl
Vinyl
78
Commercial 99/[12]
64/[3p]
4a
1b
2b
SnBu3
•
Me2SnBu2
68b
85
SnBu2
Commercial 91/[14]
2
SnBu2
7
8
2
2
Isopropenyl
Isobutenyl
89
45
–
–
3b
4b
2
SnBu2
2
SnBu2
2
9
2
2
2
Allyl
79
83
94
Commercial 78/[3p]
Commercial 78/[13]
60/[15]
5b
6bc
7b
10
11
Phenyl
Ph2SnBu2
SnBu2
p-Vinylphenyl
2
12
13
2
2
Thienyl
Benzyl
58
[16]
8b
9b
SnBu2
S
2
Bn2SnBu2
79b
81/[3o]
SnBu2
•
14
15
16
17
2
1
1
1
Propargyl
Ethyl
77
88b
73
77
[18]
10b
1c
2
Et3SnBu2
Commercial 85/[3p]
SnBu
Vinyl
[3b]
–
2c
3
SnBu
Isopropenyl
3c
3
(continued on next page)

2370
S. Lamandé-Langle et al. / Journal of Organometallic Chemistry 694 (2009) 2368–2374
Table 1 (continued)
Entry
n
R
Product
Ph3SnBu
Yielda (%)
82
Literature yield (%)/(ref)
90/[20a]
No.
SnBu
3
18
19
20
21
22
23
1
Allyl
4c
1
1
1
0
0
0
Phenyl
Benzyl
Propargyl
Allyl
63
87b
62
57
59
90
Commercial [21]
[22]
5cd
6ce
7c
Bn3SnBu
SnBu
•
–
3
Sn
4
Commercial 66/[28]
Commercial [3b]
61/[23]
1d
2d
3d
Sn
4
Vinyl
Sn
4
•
24
Allenyl
a
Estimated by 1H NMR.
Isolated yield.
10% of Ph2 was observed.
5% of Ph2 was observed.
6% of Bn2 was observed.
b
c
d
e
Bu4-nSnCln
R
H
Bu4-nSn
R
n
EtMgBr
R
MgBr
))), THF, rt, 90 min.
))), Et2O, rt
n = 2 1e-2e, n = 3 1f-2f
Scheme 2.
the sonicated preparation of EtMgBr, then synthesis of the magne-
sium acetylide by hydrogen–metal exchange and finally condensa-
tion of the latter with halogenotins using ultrasound (Scheme 2).
A clean double or triple-substitution reaction was possible and
yielded di- or tri-functional tin products, which had never
previously been described (entries 1–4). The results are presented
in Table 2.
2.3. Stille cross-coupling reaction with functional organotin
compounds
In view of the surprising lack of literature reports on the reactiv-
ity of multi-functional organotin compounds, and as we obtained
various di-, tri- and tetra-functional organotin compounds [8],
we decided to use them in a Stille cross-coupling reaction in the
presence of palladium complex catalysis [9], while monitoring
the stoichiometry of the reaction in order to ascertain how many
groups were transferred. This type of reaction has never previously
been carried out to our knowledge. Just one example of allylation
of carbonyl compounds demonstrated that a tetraallyltin can
transfer several groups [10]. We therefore carried out the Stille
cross-coupling reaction with different iodovinylic acids (or esters),
first introducing a half or a third equivalent of di- or tri-functional
organotin compounds and then adding the necessary quantity so
that the reaction was quantitative (followed by 1H NMR spectros-
copy) (Scheme 3). The results are presented in Table 3.
Table 2
Synthesis of 1-alkynyltin compounds.
Entry
1
n
R
Product
Yield (%)
No.
2
Methoxymethyl
MeO
86a
45b
1e
SnBu2
SnBu2
2
3
Me3Si
MeO
2
3
2
3
Trimethylsilyl
92a
52b
2e
1f
2
Methoxymethyl
82a
47b
SnBu
SnBu
As can been seen, we transferred more than one group, but we
could not prove that we had transferred two or three groups be-
cause we introduced a slight excess of organotin compounds so
that the reaction was complete. As it is known that it is always nec-
essary to use an excess of organotin compounds in a Stille reaction,
in the case of the allylstannanes (entry 8) we must introduced a
4
3
Trimethylsilyl
87a
55b
2f
Me3Si
3
Estimated by 1H NMR.
Isolated yield.
a
b

S. Lamandé-Langle et al. / Journal of Organometallic Chemistry 694 (2009) 2368–2374
2371
R
I
DMF, 12 h
Bu4-nSnRn
n' eq.
+
Pd(PPh3)2Cl2 (5% mol)
COOR'
COOR'
1-7g
1 eq.
R = alkenyl, aryl, alkynyl and allyl
Scheme 3.
Table 3
Reactivity of functional organotin compounds in a Stille cross-coupling reaction.
Entry
n
R
R0
n0, T °C
Product
Rdt (%)a
81
No.
1
2
Vinyl
Et
0.65, 25
1g
CO2Et
2
3
4
5
2
2
3
4
Vinyl
Vinyl
Vinyl
Vinyl
H
0.75, 25
0.6, 25
0.5, 25
0.55, 30
86
2g
2g
2g
2g
CO2H
CO2H
CO2H
CO2H
SnBu3
SnBu3
H
73b
59b
40
6
2
Isopropenyl
p-Vinylphenyl
Allyl
H
0.65, 70
0.65, 70
1.2, 60
74
89
77
89
51
3g
4g
5g
6g
7g
CO2Et
7
2
Et
Et
Et
H
CO2Et
8*
9
2
CO2Et
Me3Si
2
Trimethylsilyl ethynyl
Phenyl
0.65, 25
0.55, 60
CO2Et
10
3
CO2H
a
Isolated yield.
Deprotected with HCl 1 M.
b
*
Pd(PPh3)4 is used.
considerable excess of organotin compounds as already reported
[10].
proton resonance of CDCl3 (dH = 7.25 ppm) as the internal refer-
ence, were as follows (in order): chemical shift (d in ppm relative
to Me4Si), multiplicity (s, d, t, m, b for singlet, doublet, triplet,
multiplet, broad), coupling constants (J in Hz). 13C NMR spectra
were recorded at 50.3 MHz on the same instrument using the
CDCl3 solvent peak at dC = 77.0 ppm as reference. Mass spectra
were obtained on a Hewlett Packard (engine 5989A) in GC–MS
(70 eV) mode. The isotopic patterns are given for 120Sn (isotopic
values 33%) in organotin fragments; this means that the reported
values (values in brackets) for organotin fragments were only
roughly a third of the correct value, taking into account the 10 iso-
topes of tin compared to those of the organic fragment. IR spectra
were recorded on a Perkin–Elmer 781 Infrared Spectrophotometer
or on a Perkin–Elmer Spectrum-One. Standard column chromato-
graphy was performed on Merk silica gel (60 Å, 230–400 mesh sil-
ica gel) or on neutral alumina. DMF was dried by distillation over
calcium hydride prior to use. Tin halides (Bu3SnCl, Bu2SnCl2,
BuSnCl3, SnCl4) were commercially available and were used
In conclusion, we have described here a new procedure allow-
ing effective synthesis of various organotin compounds using
ultrasound. The main advantages of this procedure are: (a) the
quality of the reactants is not critical (solvents and tin halides)
and they do not need careful purification before use (see Section
3), (b) the use of an additive is not necessary and (c) fair to good
yields are obtained. The catalytic couplings utilizing part of these
organotin compounds enabled us to transfer more than one or
two groups, but using these di- and tri-functional organotin com-
pounds made it possible to decrease the quantity of tin and thus
the reactions were cleaner.
3. Experimental
1H NMR spectra were recorded on a Bruker AC 200 (200 MHz)
using CDCl3 as solvent. The results, reported using the residual

2372
S. Lamandé-Langle et al. / Journal of Organometallic Chemistry 694 (2009) 2368–2374
without any purification. The compounds are commercially avail-
able as 1a, 2a, 4a, 2b, 5b, 6b, 1c, 5c, 1d, 2d, 1g, 7g or fully described
as 3a [11], 4a [12], 1b [13], 2b [14], 4c [20], 1d [28], 3d [23], 2g
[24], 3g [25].
149 MHz): ꢀ67.6; MS (70 eV) m/z: organotin fragments 343
(M+ꢀC4H9, 26), 287 (23), 203 (35), 121 (10); organic fragments
57 (20), 41 (100), 39 (35).
3.1.5. Dibenzyldi-n-butyltin (9b) [17]
3.1. Preparation of mono-, di-, tri- and tetra-functional organotin
compounds (entries 1–24)
IR: 3020, 1600, 1490; 1H NMR d ppm (CDCl3, 200 MHz): 0.90 (t,
J = 7 Hz, 6H), 1.22–1.47 (m, 12H), 2.36 (s, 2JSn–H = 57 Hz, 4H), 6.97–
7.08 (m, 6H), 7.20–7.27 (m, 4H); 13C NMR d ppm (CDCl3, 50 MHz):
10.3 (1JSn–C = 312–325 Hz, 2C), 14.2 (2C), 18.9 (1JSn–C = 236–246 Hz,
2C), 27.8 (3JSn–C = 55 Hz, 2C), 29.3 (2JSn–C = 20 Hz, 2C), 123.6
A mixture of 0.49 g (0.02 at-gr) of magnesium turnings and
0.005 mol BunSnCl4ꢀn was placed in a Schlenk tube, then covered
with 5 mL of solvent (THF or Et2O) to which a few drops of pure
RX were added. The Schlenk tube was plunged into a commercial
ultrasound cleaning bath (Branson B1200 E1, working frequency:
47 kHz, 300 W). When the reaction had started, the rest of the
RX diluted in 15 mL of the solvent (C = 1.2 mol/L) was added. When
the reaction was complete, the mixture was washed with a satu-
rated solution of sodium chloride and extracted with diethyl ether.
The organic layers were dried over magnesium sulfate, the solvents
are removed under reduced pressure and the compound obtained
was purified by column chromatography on neutral alumina
(100% petroleum ether) or on silica gel (100% petroleum ether pre-
viously neutralised with triethylamine).
(5JSn–C = 13 Hz, 2C), 127.6 (3JSn–C = 22 Hz, 4C), 128.9 (4JSn–C
=
11 Hz, 4C), 143.4 (2JSn–C = 35 Hz, 2C); 119Sn NMR d ppm (CDCl3,
149 MHz): ꢀ10.6; MS (70 eV) m/z: organotin fragments 416 (M+,
2), 325 (M+ꢀC7H7, 87), 269 (48), 213 (58), 211 (100), 177 (20),
121 (14); organic fragments 91 (89), 65 (25), 39 (11).
3.1.6. Diallenyldi-n-butyltin (10b) [18]
IR: 3100, 1940; 1H NMR d ppm (CDCl3, 200 MHz): 0.94 (t,
J = 7 Hz, 6H), 1.17 (t, J = 8.1 Hz, 3H), 1.32–1.66 (m, 8H), 4.27 (d,
4
2
J = 7.1 Hz, JSn–H = 33–47 Hz, 4H), 5.07 (t, J = 7.1 Hz, JSn–H = 29 Hz,
2H); 13C NMR d ppm (CDCl3, 50 MHz): 11.9 (1JSn–C = 370–387 Hz,
2C), 14.1 (2C), 27.3 (3JSn–C = 58 Hz, 2C), 28.9 (2JSn–C = 24 Hz, 2C),
64.7 (3JSn–C = 47 Hz, 2C), 74.6 (1JSn–C = 344–362 Hz, 2C), 210.9
(2C); 119Sn NMR d ppm (CDCl3, 149 MHz): ꢀ61.8; MS (70 eV)
m/z: organotin fragments 273 (M+ꢀC3H3, 70), 255 (M+ꢀC4H9, 22),
234 (14), 217 (17), 177 (100), 161 (23), 159 (81), 121 (38); organic
fragments 41 (37), 39 (30).
3.1.1. Di-n-butyldi-isopropenyltin (3b)
IR: 3040, 1634; 1H NMR d ppm (CDCl3, 200 MHz): 0.94 (t,
J = 7.2 Hz, 6H), 1.00–1.62 (m, 12H), 2.02 (dd, J = 1.4 Hz, J = 1.5 Hz,
3JSn–H = 45 Hz, 6H), 5.17 (dq, J = 2.8 Hz, J = 1.4 Hz, 2H), 5.78 (dq,
J = 2.8 Hz, J = 1.5 Hz, 2H); 13C NMR d ppm (CDCl3, 50 MHz): 9.9
(1JSn–C = 334–351 Hz, 2C), 14.1 (2C), 27.6 (2JSn–C = 47 Hz, 2C), 27.8
(3JSn–C = 57 Hz, 2C), 29.4 (2JSn–C = 21 Hz, 2C), 126.8 (2JSn–C = 30 Hz,
2C), 149.5 (2C); 119Sn NMR d ppm (CDCl3, 149 MHz): ꢀ74.3; MS
(70 eV) m/z: organotin fragments 259 (M+ꢀC4H9, 56), 219 (11),
203 (100), 163 (41); 161 (66), 135 (15), 121 (30); organic frag-
ments 41 (81), 39 (58).
3.1.7. n-Butyltriethyltin (1c) [19]
IR: 2955, 2920, 2900, 2862; 1H NMR d ppm (CDCl3, 200 MHz):
0.66-1.05 (m, 12H), 1.17–1.61 (m, 12H); 13C NMR d ppm (CDCl3,
50 MHz): 0.4 (1JSn–C = 305–319 Hz, 3C), 8.1 (1JSn–C = 300–314 Hz),
11.4 (3C), 14.5, 27.8 (3JSn–C = 50 Hz), 29.7 (2JSn–C = 20 Hz); 119Sn
NMR d ppm (CDCl3, 149 MHz): 2.1; MS (70 eV) m/z: organotin frag-
ments 235 (M+ꢀC4H9, 49), 207 (14), 183 (17), 179 (100), 151 (54),
149 (66), 121 (36); organic fragments 41 (24), 39 (12).
3.1.2. Di-n-butyldi-isobutenyltin (4b)
IR: 3063, 1610; 1H NMR d ppm (CDCl3, 200 MHz): 0.92 (t,
J = 7.2 Hz, 6H), 1.29–1.58 (m, 12H), 1.82 (s, 6H), 1.93 (s, 6H), 5.51
(s, 2H); 13C NMR d ppm (CDCl3, 50 MHz): 11.7 (1JSn–C = 348–
365 Hz, 2C), 14.1 (2C), 26.3 (2C), 27.7 (3JSn–C = 54 Hz, 2C), 29.1
(2C), 29.6 (2JSn–C = 20 Hz, 2C), 123.2 (1JSn–C = 430–450 Hz, 2C), 152
(2C); 119Sn NMR d ppm (CDCl3, 149 MHz): ꢀ109.4; MS (70 eV) m/z:
organotin fragments 287 (M+ꢀC4H9, 54), 231 (100), 177 (20), 175
(36), 135 (40), 121 (13); organic fragments 67 (16), 55 (11), 53
(10), 41 (68), 39 (25).
3.1.8. n-Butyltrivinyltin (2c)
IR: 3042, 1630; 1H NMR d ppm (CDCl3, 200 MHz): 0.91 (t,
J = 7.1 Hz, 3H), 1.05–1.63 (m, 6H), 5.76 (dd, J = 20 Hz, J = 3.8 Hz,
3JSn–H = 81–85 Hz, 1H), 6.24 (dd, J = 13.8 Hz, J = 3.8 Hz, JSn–H
=
3
2
17.4–21.5 Hz, 1H), 6.46 (dd, J = 20 Hz, J = 13.8 Hz, JSn–H = 65–
13C NMR
d
70 Hz, 1H);
ppm (CDCl3, 50 MHz): 10.7 (1JSn–C = 391–
409 Hz), 14.1, 27.4 (3JSn–C = 58 Hz), 29.1 (2JSn–C = 22 Hz), 135.7
(3C), 137.2 (1JSn–C = 445–466 Hz, 3C); 119Sn NMR d ppm (CDCl3,
149 MHz): ꢀ123.9; MS (70 eV) m/z: organotin fragments 201
(M+ꢀC4H9, 100), 175 (44), 149 (18), 147 (55), 121 (24); organic
fragments 41 (65), 39 (32).
3.1.3. Di-n-butyldi-p-vinylphenyltin (7b) [15]
IR: 3080, 3050, 1625, 1590, 1490; 1H NMR d ppm (CDCl3,
200 MHz): 0.92 (t, J = 7.2 Hz, 6H), 1.28–1.69 (m, 12H), 5.29 (dd,
J = 0.9 Hz, J = 10.8 Hz, 2H), 5.81 (dd, J = 0.9 Hz, J = 17.6 Hz, 2H),
6.75 (dd, J = 10.8 Hz, J = 17.6 Hz, 2H), 7.42 (d, J = 8.2 Hz, 2H), 7.50
3.1.9. n-Butyltri-isopropenyltin (3c)
IR: 3038, 1633; 1H NMR d ppm (CDCl3, 200 MHz): 0.94 (t,
J = 7.1 Hz, 3H), 1.07–1.15 (m, 2H), 1.25–1.47 (m, 2H), 1.53–1.73
(d, J = 8.2 Hz, 2H); 13C NMR d ppm (CDCl3, 50 MHz): 10.8 (1JSn–C
=
353–369 Hz, 2C), 14.1 (2C), 27.8 (3JSn–C = 60 Hz, 2C), 29.4
(2JSn–C = 21 Hz, 2C), 114.4 (2C), 126.4 (3JSn–C = 45 Hz, 4C), 137.4
(2JSn–C = 33 Hz, 4C), 138.0 (2C), 140.7 (2C); 119Sn NMR d ppm
(CDCl3, 149 MHz): ꢀ64.6; MS (70 eV) m/z: organotin fragments
383 (M+ꢀC4H9, 23), 327 (32), 223 (44), 197 (15), 121 (15); organic
fragments 77 (16), 57 (14), 51 (14), 41 (100), 39 (27).
(m, 2H), 2.04 (t, J = 1.5 Hz, JSn–H = 47 Hz, 9H), 5.22 (dq, J = 2.8 Hz,
3
J = 1.5 Hz, 3JSn–H = 69 Hz, 3H), 5.82 (dq, J = 2.8 Hz, J = 1.5 Hz, 3JSn–H
=
155 Hz, 3H); 13C NMR d ppm (CDCl3, 50 MHz): 10.3 (1JSn–C = 353–
369 Hz), 14.1, 27.5 (2JSn–C = 49 Hz, 3C), 27.8, 29.3 (2JSn–C = 21 Hz),
127.7 (2JSn–C = 32 Hz, 3C), 148.6 (1JSn–C = 416–435 Hz, 3C); 119Sn
NMR d ppm (CDCl3, 149 MHz): ꢀ110.4; MS (70 eV) m/z: organotin
fragments 243 (M+ꢀC4H9, 60), 203 (48), 163 (19), 161 (50), 135
(17), 121 (27); organic fragments 41 (95), 39 (100).
3.1.4. Di-n-butyldithien-2-yltin (8b) [16]
IR: 3075, 1640; 1H NMR d ppm (CDCl3, 200 MHz): 0.99 (t,
J = 7.2 Hz, 6H), 1.39–1.82 (m, 12H), 7.25–7.45 (m, 4H), 7.73–7.80
(m, 2H); 13C NMR d ppm (CDCl3, 50 MHz): 13.2 (1JSn–C = 394–
3.1.10. n-Butyltriphenyltin (5c) [21]
IR: 3082, 1491; 1H NMR
d
ppm (CDCl3, 200 MHz): 0.91
(t, J = 7.2 Hz, 3H), 1.30–1.79 (m, 6H), 7.37–7.44 (m, 9H), 7.55–
7.60 (m, 6H); 13C NMR
ppm (CDCl3, 50 MHz): 11.3
(1JSn–C = 381–399 Hz), 14.1, 27.8 (3JSn–C = 64 Hz), 29.2 (2JSn–C
412 Hz, 2C), 14.1 (2C), 27.6 (3JSn–C = 65 Hz, 2C), 29.1 (2JSn–C
=
23 Hz, 2C), 128.5 (3JSn–C = 46 ppm, 2C), 131.8 (2JSn–C = 16 Hz, 2C),
134.7 (2C), 136.6 (3JSn–C = 31 Hz, 2C); 119Sn NMR d ppm (CDCl3,
d
=

S. Lamandé-Langle et al. / Journal of Organometallic Chemistry 694 (2009) 2368–2374
2373
22 Hz), 128.9 (3JSn–C = 47 Hz, 6C), 129.2 (4JSn–C = 11 Hz, 3C), 137.5
(2JSn–C = 35 Hz, 3C), 139.6 (1JSn–C = 460–482 Hz, 3C); 119Sn NMR d
ppm (CDCl3, 149 MHz): ꢀ97.1; MS (70 eV) m/z: organotin frag-
ments 351 (M+ꢀC4H9, 55), 197 (52), 120 (47); organic fragments
77 (38), 57 (21), 51 (72), 41 (100), 39 (36).
461 Hz, 2C), 119.7 (2JSn–C = 67 Hz, 2C); 119Sn NMR d ppm (CDCl3,
149 MHz): ꢀ158.9; MS (70 eV) m/z: organotin fragments 371
(M+ꢀC4H9, 44), 315 (10), 217 (39), 121 (10); organic fragments
97 (65), 83 (28), 73 (70), 57 (40), 45 (14), 43 (12), 41 (100), 39 (14).
3.2.3. Tri-n-butyltrimethylsilylethynyltin (1f)
3.1.11. Tribenzyl-n-butyltin (6c) [22]
IR: 2158; 1H NMR d ppm (CDCl3, 200 MHz): 0.20 (s, 9H), 0.94 (t,
J = 7.0 Hz, 9H), 1.31–1.65 (m, 18H); 13C NMR d ppm (CDCl3,
50 MHz): 0.6 (3C), 11.5 (1JSn–C = 363–380 Hz, 3C), 14.1 (3C), 27.3
(3JSn–C = 58 Hz, 3C), 29.2 (1JSn–C = 22 Hz, 3C), 113.4 (1JSn–C = 282–
IR: 3078, 3020, 1600, 1495; 1H NMR d ppm (CDCl3, 200 MHz):
2
0.84 (t, J = 7.1 Hz, 3H), 1.13–1.38 (m, 6H), 2.31 (s, JSn–H = 58 Hz,
6H), 6.88–7.05 (m, 9H), 7.22 (td, J = 7.6 Hz, J = 1.5 Hz, 6H); 13C
NMR d ppm (CDCl3, 50 MHz): 10.7 (1JSn–C = 329–340 Hz), 14.1,
294 Hz), 119.1 (2JSn–C = 38 Hz); 119Sn NMR
d ppm (CDCl3,
19.2 (1JSn–C = 241–253 Hz, 3C), 27.7 (3JSn–C = 57 Hz), 29 (2JSn–C
=
149 MHz): ꢀ66.6; MS (70 eV) m/z: organotin fragments 331
(M+ꢀC4H9, 48), 275 (34), 219 (30), 217 (49), 203 (11), 121 (10); or-
ganic fragments 97 (58), 73 (22), 57 (35), 41 (100), 39 (19).
20 Hz), 123.9 (5JSn–C = 13 Hz, 3C), 127.8 (4JSn–C = 23 Hz, 6C), 129
(3JSn–C = 11 Hz, 6C), 142. 7 (2JSn–C = 35 Hz, 3C); 119Sn NMR d ppm
(CDCl3, 149 MHz): ꢀ21.2; MS (70 eV) m/z: organotin fragments
359 (M+ꢀBn, 6), 211 (54), 121 (6), 120 (13); organic fragments
91 (100), 65 (31), 39 (16).
3.2.4. Tri-n-butyl-3-methoxypropynyltin (2f)
IR: 2160, 1105; 1H NMR d ppm (CDCl3, 200 MHz): 0.93 (t,
4
J = 7.1 Hz, 9H), 1.27–1.65 (m, 18H), 3.42 (s, 3H), 4.14 (s, JSn–H
=
3.1.12. Triallenyl-n-butyltin (7c)
8.5 Hz, 2H); 13C NMR d ppm (CDCl3, 50 MHz): 11.4 (1JSn–C = 366–
IR: 3092; 1H NMR d ppm (CDCl3, 200 MHz): 0.95 (t, J = 7.1 Hz,
383 Hz, 3C), 14.1 (3C), 27.4 (3JSn–C = 60 Hz, 3C), 29.3 (2JSn–C
23 Hz, 3C), 57.6, 61.0, 90.3 (1JSn–C = 305–319 Hz), 106.0 (2JSn–C
=
=
4
3H), 1.30–1.71 (m, 6H), 4.36 (d, J = 7.1 Hz, JSn–H = 44–46 Hz, 6H),
2
5.12 (t, J = 7.1 Hz, JSn–H = 32 Hz, 3H); 13C NMR d ppm (CDCl3,
55 Hz); 119Sn NMR d ppm (CDCl3, 149 MHz): ꢀ61.2; MS (70 eV)
m/z: organotin fragments 303 (M+ꢀC4H9, 59), 247 (48), 191 (14),
189 (26), 159 (29), 121 (16); organic fragments 57 (20), 41 (100),
39 (35).
50 MHz): 11.9 (1JSn–C = 373–388 Hz), 14.1, 27.1 (3JSn–C = 61 Hz),
28.5 (2JSn–C = 27 Hz), 66 (3JSn–C = 54 Hz, 3C), 74.6 (1JSn–C = 413–
433 Hz, 3C), 211.7 (3C); MS (70 eV) m/z: organotin fragments 255
(M+ꢀC3H3, 19), 159 (100), 121 (17); organic fragments 41 (57),
39 (100), 38 (22).
3.3. Stille cross-coupling reaction with functional stannanes (entries
1–7g)
3.2. Preparation of 1-alkynyltin compounds (entries 1–4, Table 2)
Dichlorobis(triphenylphosphine)palladium II (5 mol%) was
added to an anhydrous DMF solution (2 mL) of acid or ester halide
(1.5 mmol) in a Schlenk flask under argon, and n0 mmol of di- or tri-
functional organotin compounds were added after stirring for
15 min. The mixture was stirred for12 h at the recommended tem-
perature. After cooling, the reaction mixture was filtered through a
Celite path and then treated with a 1 M solution of potassium fluo-
ride and ethylacetate to eliminate the tributyltin iodide thus
formed. The aqueous layer was extracted with diethyl ether. The
organic layer was washed with brine to eliminate the DMF and
dried over MgSO4. After evaporation of the solvents, the crude
product was purified by column chromatography on silica gel
(90/10: petroleum ether/diethyl ether) in the case of ethylic esters,
and by an acid–base treatment for the acid and stannic esters,
which were deprotected at the same time.
A mixture of 2.18 g (0.02 mol) bromoethane, 0.49 g (0.02 at-gr)
of magnesium turnings in 17 mL of anhydrous diethyl ether was
placed in a dry round-bottomed three-necked flask (100 mL)
equipped with a condenser and a dropping funnel flushed with ar-
gon. The round-bottomed flask were plunged into a commercial
ultrasound cleaning bath (Branson B1200 E1, working frequency:
47 kHz, 300 W). When the magnesium had disappeared, 0.04 mol
1-alkynes diluted in anhydrous diethyl ether were added dropwise.
When the reaction had finished, approximately 10 mL anhydrous
THF was poured in and when the solution was quite homogeneous,
14 mmol Bu3SnCl (or 7 mmol Bu2SnCl2) diluted in an equivalent
volume of THF was added dropwise. When the reaction was com-
plete, the mixture was washed with a saturated solution of sodium
chloride and extracted with diethyl ether. The organic layers were
dried over magnesium sulfate, solvents were removed under re-
duced pressure and the compound obtained was purified by col-
umn chromatography on neutral alumina (100% petroleum ether)
or on silica gel (100% petroleum ether, previously neutralised with
triethylamine).
3.3.1. (2E)-Ethyl-3-(p-vinylphenyl)-prop-2-enoate (4g) [25]
IR: 3050, 3088, 1728, 1644, 1608, 1568, 1509; 1H NMR d ppm
(CDCl3, 200 MHz): 1.36 (t, J = 7.1 Hz, 3H), 4.28 (q, J = 7.1 Hz, 2H),
5.33 (dd, J = 10.9 Hz, J = 0.7 Hz, 1H), 5.82 (dd, J = 17.6 Hz,
J = 0.7 Hz, 1H), 6.44 (d, J = 16 Hz, 1H), 6.73 (dd, J = 17.6 Hz,
J = 10.9 Hz, 1H), 7.43 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H),
7.68 (d, J = 16 Hz, 1H); 13C NMR d ppm (CDCl3, 50 MHz): 14.8,
60.9, 115.7, 118.4, 127.1 (2C), 128.7 (2C), 134.3, 136.5, 139.9,
144.5, 167.5; MS (70 eV) m/z: 202 (65), 174 (18), 173 (10), 158
(10), 157 (76), 130 (54), 129 (68), 128 (100), 127 (45), 115 (14),
103 (12), 102 (28), 77 (51), 76 (14), 75 (15), 64 (14), 63 (23), 51
(43), 50 (18), 43 (11), 39 (18).
3.2.1. Di-n-butyl-bis(3-methoxypropynyl)tin (1e)
IR: 2165; 1H NMR d ppm (CDCl3, 200 MHz): 0.95 (t, J = 7.2 Hz,
4
6H), 1.19–1.72 (m, 12H), 3.42 (s, 6H), 4.15 (s, JSn–H = 9.3 Hz); 13C
NMR d ppm (CDCl3, 50 MHz): 13.6 (1JSn–C = 464–485 Hz, 2C), 13.9
(2C), 26.8 (3JSn–C = 70 Hz, 2C), 28.6 (2JSn–C = 28 Hz, 2C), 58 (2C),
60.8 (2C), 87.1 (1JSn–C = 475–497 Hz, 2C), 106.5 (2JSn–C = 95 Hz,
2C); 119Sn NMR d ppm (CDCl3, 149 MHz): ꢀ146.2; MS (70 eV)
m/z: organotin fragments 315 (M+ꢀC4H9, 18), 189 (13), 159 (22),
151 (37), 121 (8); organic fragments 69 (13), 57 (29), 45 (12), 41
(100), 39 (45).
3.3.2. (2E)-Ethyl hexa-2,5-dienoate (5g) [26]
IR: 3062, 3081, 1730, 1660, 1646; 1H NMR d ppm (CDCl3,
200 MHz): 1.29 (t, J = 7.1 Hz, 3H), 2.95 (tq, J = 6.5 Hz, J = 1.5 Hz,
2H), 4.19 (q, J = 7.1 Hz, 2H), 5.05–5.16 (m, 2H), 5.76–5.92 (m,
2H), 6.98 (dt, J = 15.6 Hz, J = 6.5 Hz, 1H); 13C NMR d ppm (CDCl3,
50 MHz): 14.6, 36.5, 60.6, 117.6, 122.6, 134.3, 146.8, 166.9; MS
(70 eV) m/z: 140 (MÅ+, 3), 97 (11), 95 (24), 68 (11), 67 (100), 66
(22), 65 (18), 41 (60), 40 (15), 39 (69).
3.2.2. Di-n-butyl-bis(trimethylsilylethynyl)tin (2e)
IR: 2152; 1H NMR d ppm (CDCl3, 200 MHz): 0.21 (s, 18H), 0.95
(t, J = 7.2 Hz, 6H), 1.17–1.72 (m, 12H); 13C NMR d ppm (CDCl3,
50 MHz): 0.4 (6C), 13.9 (1JSn–C = 457–478 Hz, 2C), 14.0 (2C), 26.8
(3JSn–C = 67 Hz, 2C), 28.6 (2JSn–C = 27 Hz, 2C), 109.6 (1JSn–C = 442–

2374
S. Lamandé-Langle et al. / Journal of Organometallic Chemistry 694 (2009) 2368–2374
[6] (a) C. Einhorn, J. Einhorn, J.L. Luche, Synthesis (1989) 787–813;
(b) S.V. Ley, C.M.R. Low, Ultrasound in Synthesis, Springer, New York, 1989;
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3.3.3. (2E)-Ethyl-5-trimethylsilyl-pent-2-en-4-ynoate (6g) [27]
IR: 3320, 3071, 3082, 2125, 1729, 1621; 1H NMR d ppm (CDCl3,
200 MHz): 0.23 (s, 9H), 1.31 (t, J = 7.1 Hz, 3H), 4.23 (q, J = 7.1 Hz,
2H), 6.26 (d, J = 16 Hz, 1H), 6.76 (d, J = 16 Hz, 1H); 13C NMR d
ppm (CDCl3, 50 MHz): 0.02 (3C), 14.6, 61.2, 101.7, 105.3, 125.3,
131.6, 166.2.
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Acknowledgments
We thank the CNRS and MRT for providing financial support,
and the ‘‘Service d’analyse chimique du Vivant de Tours” for
recording NMR and mass spectra.
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