Stereoselective hydrostannation of substituted alkynes with trineophyltin hydride

Article abstract of DOI:10.1016/S0022-328X(02)01213-5

Hydrostannation of mono- and disubstituted alkynes with trineophyltin hydride (1) leads to vinylstannes in good to excellent yields the configuration of the products depending on the reaction conditions. Thus, whereas hydrostannation under radical conditi

Full text of DOI:10.1016/S0022-328X(02)01213-5

Journal of Organometallic Chemistry 650 (2002) 173–180
www.elsevier.com/locate/jorganchem
Stereoselective hydrostannation of substituted alkynes with
trineophyltin hydride
Vero´nica I. Dodero, Liliana C. Koll 1, Sandra D. Mandolesi, Julio C. Podesta´ *,1
Departamento de Qu´ımica, Instituto de In6estigaciones en Qu´ımica Orga´nica, Uni6ersidad Nacional del Sur, A6enida Alem 1253,
8000 Bah´ıa Blanca, Argentina
Received 2 August 2001; accepted 9 January 2002
Abstract
Hydrostannation of mono- and disubstituted alkynes with trineophyltin hydride (1) leads to vinylstannanes in good to excellent
yields, the configuration of the products depending on the reaction conditions. Thus, whereas hydrostannation under radical
conditions leads stereoselectively to only one of the two possible products corresponding to an anti addition in 60–99% yield, the
1
additions catalyzed by bis(triphenylphosphine)palladium dichloride gave mixtures of the syn adducts (60–79% yield). Full H-,
13C-, and 119Sn-NMR as well as mass spectra data of the organotin adducts are given. © 2002 Elsevier Science B.V. All rights
reserved.
Keywords: Hydrostannation; Vinylstannanes; Radical; Palladium catalysis; Stereoselectivity
ductions and additions [3]. In this paper, we report the
results obtained in the addition of trineophyltin hydride
1. Introduction
(1) [3a] to mono- and disubstituted alkynes under radi-
cal and palladium catalyzed conditions.
Vinylstannanes are very useful intermediates in or-
ganic synthesis, especially when they have a well
defined stereochemistry [1]. Among other important
applications, they are used as vinyl anion equivalents,
as precursors of vinyllithiums, and in cross-coupling
2. Results and discussion
reactions (the Stille reaction). Hydrostannation of alky-
According to previous reports on the addition of
nes is still the more simple and economical method for
organotin hydrides to acetylenes, we expected that
the preparation of vinylstannanes. However, in recent
whereas the hydrostannation under radical conditions
publications it has been stated that the main problems
would lead to a mixture of mainly the two regioisomers
resulting from an anti attack (A-1 and A-2), the palla-
dium catalyzed reactions would yield mainly two re-
gioisomers corresponding to a syn addition (S-1 and
of radical hydrostannation are the low yields [2a,2] and
that the regio- and stereoselectivities are low [2b,2c]. It
has also been stated that, depending on the structure of
the alkynes, regio- and stereoselectivities could not be
S-2), as shown in Scheme 1.
predicted under radical conditions [2c].
We are interested in the synthesis of organotin hy-
drides with bulky organic ligands and in their chemical
properties, especially with regard to the effect of the
volume of these ligands on the stereochemistry of re-
* Corresponding author. Tel.: +54-91-26420/280345; fax: +54-
291-4595187.
E-mail address: jpodesta@criba.edu.ar (J.C. Podesta´).
1 Member of the National Research Council (CONICET), Ar-
Scheme 1. Possible adducts resulting from the hydrostannation of
gentina.
substituted alkynes with trineophyltin hydride (1).
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(02)01213-5

174
V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
tions studied, and methyl propiolate under appropriate
We first carried out the addition of trineophyltin
conditions, E-adducts were de soles products. The for-
mation of the E-adducts 2, 5 and 11, could be ex-
plained taking into account that the known
isomerization of the initially formed kinetic Z-products
by further addition/elimination of the stannyl radical
would lead to the thermodynamically more stable E-
vinylstannanes [2c,4].
hydride (1) under free radical conditions: nitrogen at-
mosphere, 0.01 equivalents of azobisisobutyronitrile
(AIBN), without solvent at 90 °C (Section 3.1.1) or in
toluene at the same temperature (Section 3.1.2), and
UV irradiation in toluene (Section 3.1.3) to a series of
eight substituted alkynes. The results obtained are sum-
marized in Table 1.
This table shows that, according to the reaction
conditions, the addition of 1 to propargyl alcohol,
methyl propiolate, diphenylethyne, 3-phenyl-2-propyn-
1-ol, 2-butyn-1-ol, and methyl 3-phenylpropiolate leads
almost exclusively to the Z-vinylstannanes resulting
from an anti attack. In Table 1, it could also be seen
that in the additions to phenylethyne and dimethyl
acetylenedicarboxylate under the three radical condi-
The geometry assigned to compounds 3, 4, and 6–10
follows from the large 3J(Sn,H) coupling constants,
mostly well over 110 Hz, that indicate the existence of
trans HꢀCꢀCꢀSn linkages in these compounds. The
3
observed J(Sn,H) coupling constants for compounds
2, 5 and 11 —between 23 and 75 Hz (Table 2)—clearly
indicate the existence of a cis HꢀCꢀCꢀSn linkage in
these compounds. These structures were confirmed by
1
other H- and 13C-NMR data.
Table 1
Trienophyltin hydride radical addition to substituted alkynes
Compound number
Method a Time (h)
R1
R2
A-1 (%)
A-2 (%)
S-1 (%)
Yield b (%)
119Sn c (ppm)
2
2
2
3
3
3
A
B
C
A
B
C
A
1
5
H
H
H
H
H
H
H
Ph
Ph
Ph
CH2OH
CH2OH
CH2OH
COOMe
100 d
99
99
100
69
55
49
−93.7
100 d
100 d
0.5
6
10
26
1
100
100
100
34 (4)
−97.5
4 and 5
66 e
87
4: −92.4
5: −83.5
(5)
(5)
4 and 5
B
1
H
COOMe
91 (4)
9 e
65
5
6
6
6
7
7
7
C
A
B
C
A
B
C
A
0.75
H
Ph
Ph
Ph
CH2OH
CH2OH
CH2OH
CH2OH
COOMe
Ph
Ph
Ph
Ph
Ph
Ph
Me
100 e
100
70
41
5
14
72
5
6
10
9
100
100
−89.0
f
100
100
100
88 (9)
61
75
22
60
−88.8
8 and 9
12 (8)
8: −93.2
9: −94.4
9
9
B
C
A
B
C
A
B
C
24
19
2
2
1
2
3
1
CH2OH
CH2OH
Ph
Ph
Ph
COOMe
COOMe
COOMe
Me
Me
100
55
f
10
10
10
11
11
11
COOMe
COOMe
COOMe
COOMe
COOMe
COOMe
100
100
100
80
68
100
80
88
100
−81.7
100
100
100
−80.7
a The reaction were carried out under a nitrogen atmosphere; ratio hydride/alkyne=1. Method A, AIBN 0.01 equivalents, heating at 90 °C
without solvent. Method B, AIBN 0.01 equivalents, heating at 90 °C in Toluene. Method C, UV irradiation in toluene.
b Yields of products isolated from the column chromatography.
c In CDCl3; in ppm with respect to Me4Sn.
d The product isolated was (E)-1-trineophylstannyl-2-phenylethylene (2), see text.
e See text.
f No adduct formation observed.

V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
175
Table 2
Trineophyltin hydride palladium-catalized additions to substituted alkynes a
Compound no.
R1
R2
S-1 (%) b
S-2 (%) b
70 (14)
Yield c (%)
119Sn d (ppm)
12
Ph
H
H
100
30 (13)
99
67
−79.8
13 and 14
CH2OH
13: −84.7
14: −85.6
−72.3
15
Ph
CH2OH
Ph
Ph
100
67 (16)
79
60
16 and 17
33 (17)
47 (19)
69 (20)
67 (22)
16: −77.2
17: −77.6
18: −82.5
19: −76.4
9: −83.5
20: −76.8
21: −55.6
22: −68.1
−80.7
18 and 19
5 and 20
21 and 22
11
CH2OH
H
Me
53 (18)
31 (5)
33 (21)
100
70
82
70
94
COOMe
COOMe
COOMe
Ph
COOMe
a The reaction were carried out under a nitrogen atmosphere in THF; ratio hydride/alkyne=1; PdCl2(Ph3P)2: 2%; reaction time: 30 min.
b By integration of the 119Sn-NMR spectrum.
c Yields of products isolated from the column chromatography.
d In CDCl3.
The addition of trineophyltin hydride (1) to the same
eight alkynes at r.t. in THF containing 2% of bis(t-
riphenylphosphine)palladium(II) chloride led, after 30
min of reaction, in most cases to mixtures of adducts.
The results obtained are summarized in Table 2. This
Table shows that all the regioisomers formed are those
resulting from a syn attack (Scheme 1, S-1 and S-2).
The stereochemistry of compounds 11–22 was as-
same alkynes, also takes place stereoselectively but
leads in all cases to the products of a syn attack, mainly
as a mixture of the two possible regioisomers in good to
excellent yields (60–99%).
The chemical reactivity of the new vinyltrineophyl-
stannanes is similar to that of other vinyltriorganostan-
nanes. Thus, the iododestannylation of (E)-1-trineo-
phylstannyl-2-phenylethene (2) leads to (E)-b-
iodostyrene [6] in 82% yield and the Stille reaction of 2
with bromobenzene gives trans-stilbene in 86% yield.
Further investigations in order to study the effect of
changes of catalyst, alkyne, and the size of the ligands
of the organotin hydrides on the stereochemistry of
these additions are in progress.
3
signed taking into account that the observed J(Sn,H)
coupling constants were in the range 65–85 Hz, clearly
indicating a cis arrangement of the proton attached to
vinyl carbon 2 and the trineophyltin moiety attached to
1
vinyl carbon 1 of these adducts. Other H- and 13C-
NMR data confirmed also the assigned structures (Ta-
bles 3 and 4).
These results clearly demonstrate that, contrary to
what has previously been stated [2a,2b,2c], it is possible
using organotin hydrides with bulky organic ligands
such as 1 to carry out radical hydrostannation of
mono- and disubstituted alkynes with very good to
excellent stereoselectivities. The anti-addition products
were mainly obtained in satisfactory to excellent yields
(55–100%), and in only one case a mixture of the two
3. Experimental
The NMR spectra were determined partly at Dort-
mund University (Germany) (1H, 13C and 119Sn) using a
Bruker AM 300 instrument, and partly at IQUIOS
(Rosario, Argentina) with a Bruker AC 200 instrument.
Mass spectra were obtained using a Finnigan MAT
Model 8230 at Dortmund University. Irradiations were
conducted in a reactor equipped with four 250-W lamps
with peak emission at 350 nm (Philips Model HPT)
water cooled. All the solvents and reagents used were
analytical reagent grade. Trineophyltin hydride (1) was
prepared as described [7]. Phenylacetylene, dipheny-
lacetylene, propiolic acid, phenylpropiolic acid,
acetylenedicarboxylic acid, propargyl alcohol, 2-butyn-
1-ol, and bis(triphenylphosphine) palladium(II) chloride
possible regioisomers in
observed.
a ratio 9/8=7.33 was
It should be noted that in a recent publication it has
been reported that the radical addition of tri-n-butyltin
hydride to the 3-phenyl-2-propyne-1-ol leads to a mix-
ture of (E)- and (Z)-3-phenyl-2-propen-1-ol (ratio E/
Z=61:39) in 72% yield [5].
On the other hand, the addition of 1 catalyzed by
bis(triphenylphosphine) palladium(II) chloride to the

176
V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
procedures before using. The methyl esters of the acids
were obtained following known techniques [8]. Phenyl-
propargyl alcohol was obtained by reduction of methyl
phenylpropiolate with lithiumaluminium hydride [9].
All the reactions were carried out following the same
procedure. One experiment is described in detail in
order to illustrate the methods used.
3.1. Addition of trineophyltin hydride (1) to substituted
alkynes under radical conditions
3.1.1. Method A
Methyl propiolate (0.15 g, 1.78 mmol) was treated
for 1 h with hydride 1 (0.924 g, 1.78 mmol) under
nitrogen at 90 °C and with AIBN as a catalyst (this
Table 3
13C-NMR data of vinyltin adducts 2–22 a
Compound no.
R1
R2
C(1)
C(2)
R1 b
R2 b
*
c
d
e
f
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
H
H
H
H
Ph
134.89 (447.0)
134.09 (366.0)
158.26 (320.7)
159.94 (315.7)
151.89 (311.7)
148.32 (332.7)
144.73 (367.6)
144.95 (371.0)
141.01 (314.8)
161.88 (416.9)
150.87 (375.1)
130.29 (425.4)
155.53 (336.3)
139.25 (24.0)
145.49 (320.6)
150.62 (346.3)
137.89 (nd)
145.24 (35.0)
144.63 (25.2)
133.48 (13.7)
133.25 (15.6)
143.77 (20.4)
138.74 (16.2)
139.14 (26.3)
136.11 (24.3)
152.84 (21.2)
128.28 (16.5)
128.07 (11.7)
144.39 (24.2)
122.53 (21.4)
148.29 (324.0)
138.91 (31.1)
140.46 (24.1)
(138.46 (27.2)
139.28 (27.2)
135.63 (25.3)
141.18 (14.2)
124.19 (13.5)
140.95 (10.7)
65.41 (37.9)
167.88 (13.7)
164.0 (35.4)
149.09 (29.1)
140.20 (22.3)
64.68 (37.0)
20.65 (36.9)
138.47 (16.3)
163.58 (no)
CH2OH
COOMe
COOMe
Ph
Ph
CH2OH
Me
Ph
COOMe
H
CH2OH
H
H
g
h
i
Ph
CH2OH
Me
CH2OH
COOMe
COOMe
Ph
140.11 (19.4)
69.55 (52.5)
20.6 (46.5)
70.18 (48.6)
172.26 (12.7)
172.69 (no)
151.29 (11.7)
j
k
l
m
n
o
u
p
q
r
H
66.04 (68.0)
CH2OH
COOMe
Ph
CH2OH
Ph
Me
CH2OH
Ph
68.49 (58.3)
171.61 (14.3)
152.16 (35.2)
143.86 (26.9)
63.80 (29.2)
18.62 (42.8)
62.40 (31.1)
137.11 (46.8)
172.71 (17.9)
Ph
Ph
137.64 (60.2)
60.69 (52.5)
152.49 (19.5)
59.04 (62.2)
14.99 (58.3)
173.71 (38.4)
144.62 (16.3)
CH2OH
CH2OH
Me
COOMe
Ph
s
143.45 (381.0)
146.70 (410.1)
141.85 (256.3)
164.14 (nd)
t
v
w
COOMe
a In CDCl3; chemical shifts, l, in ppm with respect to IMS; nJ(Sn,C) coupling constants, in Hz On brackets); nd, not determined.
b When R1 and R2=pH=chemical shift of the ipso carbon.
* Other signals:
c 32.07 (335.3); 32.85 (35,0); 38.11 (18.4); 125.35; 125.42; 127.04; 127.84; 127.97; 128.04; 151.69 (27.2).
d 32.36 (336.3); 32.98 (35.9); 38.06 (19.4); 125.32; 125.38; 127.92; 151.06 (20.4).
e 32.5 (349.8); 32.9 (36.9); 38.0 (19.4); 125.8; 125.9; 143.0; 152.0.
f 30.5 (339.2); 32.9 (37.0); 36.9 (19.2); 124.1; 124.6; 132.5; 150.0.
g 32.34 (321.0); 32.44 (33.0); 37.82 (18.5); 125.25; 125.35; 125.44; 127.05; 127.26; 127.87; 127.92; 128.10; 128.54; 151.69 (27.2).
h 31.94 (344.6); 32.70 (35.0); 37.94 (19.4); 125.34; 125.37; 126.79; 127.88; 128.00; 128.43; 151.38 (24.3).
i 32.00 (307.9); 32.93 (36.2); 38.08 (19.2); 125.15; 125.44; 128.30; 151.29.
j 31.64 (323.4); 32.80 (35.0); 38.02 (18.5); 125.34; 125.42; 127.87; 151.38 (22.4).
k 32.33 (34.0); 33.16 (327.2); 37.86 (18.5); 51.57; 125.24; 125.29; 127.81; 128.00; 128.27; 132.83; 151,58 (32.1).
l 31.13 (332.7); 32.9 (42.8); 37.55 (19.2); 51.02; 50.12; 125.12; 125.6; 128.09; 150.04.
m 31.23 (330.5); 33.10 (36.9); 38.01 (17.5); 125.20; 125.24; 125.43; 125.44; 125.92; 126.68 (15.6); 128.01; 128.32; 128.41 (27.2); 150.49 (21.4).
n 31.18 (340.2); 33.11 (36.9); 38.04 (19.4); 125.36; 125.42; 127.97; 151.27 (19.4).
o 30.70 (330.4); 33.22 (38.9); 37.96 (19.4); 125.45; 127.96; 151,04 (17.5).
p 31.4 (334.5); 32.9 (36.7); 38.3 (19.0); 125.2; 125.3; 127.8; 151.6.
q 30.75 (322.7); 33.21 (38.9); 37.89 (19.4); 125.04; 15.42; 125.46; 126.43; 126.50; 127.80; 128.04; 128.53; 129.04; 151.27 (17.5).
r 30.84 (325.8); 33.15 (36.9); 37.85 (18.5); 125.13; 125.29; 126.53 (14.9); 127.90; 127.92; 151.13 (18.5).
s 32.07 (314.9); 33.26 (36.9); 38.24 (19.4); 125.50; 125.62; 126.61; 127.99; 128.77; 130.86; 151.38 (19.5).
t 30.68 (322.7); 33.27 (36.9); 37.95 (17.5); 125.36; 125.45; 127.96; 151.27 (17.5).
u 31.39 (326.6); 33.20 (36.9); 38.10 (19.4); 125.36; 125.55; 127.88; 151.38 (17.5).
v 31.36 (340.2); 33.14 (40.5); 37.70 (18.5); 51.09; 125.32; 125.47; 127.48; 127.78; 127.89; 128.03; 128.23; 128.45; 130.56; 132.86; 150.85 (19.2).
w 30.56 (333.0); 33.14 (38.3); 37.69 (18.5); 50.78; 125.27; 125.48; 128.03; 128.15; 150.72 (17.7).

V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
177
optimal time of reaction was indicated by earlier exper-
iments in which the reaction was monitored by taking
samples at intervals and observing the disappearance of
the SnꢀH absorption by IR). The 119Sn-NMR spectrum
of the crude product showed that it consisted of a
mixture of two compounds: methyl (Z)-3-(trineophyl-
stannyl)propenoate (4), peak at −92.4 ppm, (34%),
and (E)-3-(trineophylstannyl)propenoate (5), peak at
−83.5 ppm, (66%). Flash chromatography (silica gel
60) of the mixture afforded 4 (0.31 g, 0.52 mmol,
29.6%) and 5 (0.62 g, 1.02 mmol, 57.4%), in the frac-
tions eluted with hexane/diethyl ether (97:3).
solvent was distilled off under reduced pressure. The
119Sn-NMR spectrum showed that under these condi-
tions a mixture of two compounds was formed: methyl
(Z)-3-(trineophylstannyl)propenoate (4) (91%) and
methyl (E)-3-(trineophylstannyl)propenoate (5) (9%).
Flash chromatography (silica gel 60) of the mixture
afforded 4 (0.65 g, 1.08 mmol, 59.2%) and 5 (0.04 g,
0.067 mmol, 5,8%), in the fractions eluted with hexane/
diethyl ether (97:3).
3.1.3. Method C
A solution of methyl propiolate (0.15 g, 1.78 mmol)
and 1 (0.924 g, 1.78 mmol) in dry toluene (15 ml) under
nitrogen was irradiated at room temperature (r.t.) dur-
ing 45 min. The solvent was distilled off under reduced
pressure. The 119Sn-NMR spectrum showed that under
these conditions only methyl (E)-3-(trineophylstan-
nyl)propenoate (5) in quantitative yield was obtained.
3.1.2. Method B
To a solution of methyl propiolate (0.15 g, 1.78
mmol) and AIBN (0.0023 g) in dry toluene (15 ml)
under nitrogen was added 1 (0.924 g, 1.78 mmol) and
the mixture was heated at 90 °C during 1 h. The
Table 4
1H-NMR spectra of compounds 2–22
Number Chemical shifts (l, in ppm)
2
3
4
5
0.85 (s, 3H, 2J(Sn,H) 48.7); 0.87 (s, 3H, 2J(Sn,H) 50.7); 1.09 (s, 9H); 1.10 (s, 9H); 5.55 (d, 1H, 3J(H,H) 14.1; 2J(Sn,H) 63.0);
5.56 (d, 1H, 3J(H,H) 14.1; 3J(Sn,H) 64.0); 6.83–7.42 (m, 20H)
0.97 (s, 6H, 2J(Sn,H) 49.7); 1.13 (s, 18H); 3.69 (m, 2H); 5.42 (d, 1H, 3J(H,H) 12.8; 2J(Sn,H) 69.1); 6.17 (dt, 1H, 3J(H,H) 6.3;
3J(H,H) 12.8; 3J(Sn,H) 142.1); 7.05–7.25 (m, 15H)
1.10 (s, 2H); 1.15 (s, 6H); 3.61 (s, 3H); 6.17 (d, 1H, 3J(H,H) 13.3; 2J(Sn,H) 119.4); 6.24 (d, 1H, 3J(H,H) 13.3; 3J(Sn,H) 169.1);
7.03–7.22 (m, 5H)
0.91 (s, 2H); 1.10 (s, 6H); 3.65 (s, 3H); 5.80 (d, 1H, 3J(H,H) 19.3; 2J(Sn,H) 56.7); 5.82 (d, 1H, 3J(H,H) 19.3; 3J(Sn,H) 74.9);
6.83–7.30 (m, 5H)
6
7
8
0.88 (s, 6H, 2J(Sn,H) 50.4); 0.98 (s, 18H); 6.97–7.26 (m, 26H)
0.99 (s, 6H, 2J(Sn,H) 50.7); 1.03 (s, 18H); 3.87 (bs, 2H, 3J(Sn,H) 26.8); 5.17 (s, 1H, 3J(Sn,H) 177.2); 7.00–7.30 (m, 20H)
1.15 (s, 6H, 2J(Sn,H) 48.8); 1.20 (s, 18H); 1.80 (d, 3H, 4J(H,H) 1.1; 3J(Sn,H) 42.3); 3.70 (m, 2H); 5.96 (tq, 1H, 4J(H,H) 1.1,
3J(H,H) 6.7, 3J(Sn,H) 143.3); 6.84–7.36 (m, 15H)
9
1.12 (s, 6H, 2J(Sn,H) 50.4); 1.14 (s, 18H); 1.48 (d, 3H, 3J(H,H) 6.8); 3.85 (bs, 2H, 3J(Sn,H) 38.1); 6.00 (qt, 1H, 4J(H,H) 1.5;
3J(H,H) 6.8; 3J(Sn,H) 127.5); 7.05–7.21 (m, 15H)
10
11
12
1.02 (s, 18H); 1.05 (s, 6H, 2J(Sn,H) 49.9); 3.63 (s, 3H); 6.70–7.62 (m, 20H); 8.16 (s, 1H 3J(Sn,H) 107.1)
0.95 (s, 2H); 1.08 (s, 6H); 3.65 (s, 3H); 3.75 (s, 3H); 5.58 (s, 1H, 3J(Sn,H) 23.2); 6.95–7.25 (m, 5H)
0.93 (s, 3H, 2J(Sn,H) 48.7); 0.95 (s, 3H, 2J(Sn,H) 49.7); 1.14 (s, 9H); 1.16 (s, 9H); 5.20 (d, 1H, 2J(H,H) 2.5, 3J(Sn,H) 65.3); 5.70
(d, 1H, 2J(H,H) 2.5, 3J(Sn,H) 135.5); 6.80–7.28 (m, 20H)
13
14
15
0.95 (s, 6H, 2J(Sn,H) 50.7); 1.14 (s, 18H); 3.78 (m, 2H); 5.23 (dt, 1H, 4J(H,H) 1.76, 3J(H,H) 18.8, 2J(Sn,H) 76.0); 5.58 (dt, 1H,
3J(H,H) 4.5, 3J(H,H) 18.8, 3J(Sn,H) 67.7); 6.91–8.38 (m, 15H)
0.98 (s, 6H, 2J(Sn,H) 50.2); 1.14 (s, 18H); 3.68 (m, 2H, 3J(Sn,H) 25.1); 5.01 (dt, 1H, 4J(H,H) 1.8, 2J(H,H) 1.8, 3J(Sn,H) 70.2);
5.63 (dt, 1H, 4J(H,H) 2.0, 2J(H,H) 1.8, 3J(Sn,H) 137.5); 6.94–7.26 (m, 15H)
1.00 (s, 2H); 1.09 (s, 6H); 3.58 (s, 3H); 5.55 (d, 1H, 3J(H,H) 2.4; 2J(Sn,H) 56.9); 6.52 (d, 1H, 3J(H,H) 2.4; 3J(Sn,H) 26.7);
6.98–7.21 (m, 5H)
16
17
0.87 (s, 6H, 2J(Sn,H) 48.2); 1.02 (s, 18H); 6.35 (s, 1H, 3J(Sn,H) 69.3); 6.66–7.27 (m, 25H)
0.88 (s, 18H); 1.11 (s, 6H, 2J(Sn,H) 64.4); 3.76 (d, 2H, 3J(H,H) 6.1), 5.49 (t, 1H, 3J(H,H) 6.1, 3J(Sn,H) 77.4); 6.57–6.69 (m, 5H);
6.85–7.32 (m, 15H)
18
19
20
1.13 (s, 6H, 2J(Sn,H) 54.2); 1.18 (s, 18H); 3.90 (m, 2H, 3J(Sn,H) 42.7); 5.20 (s, 1H); 6.39 (bs, 1H, 3J(Sn,H) 85.3); 7.20–7.54 (m,
20H)
0.95 (s, 6H, 2J(Sn,H) 49.2); 1.11 (s, 18H); 1.40 (s, 3H, 3J(Sn,H) 47.7); 3.95 (d, 2H, 3J(H,H) 5.8); 5.33 (t, 1H, 3J(H,H) 5.8,
3J(Sn,H) 85.3); 6.97–7.25 (m, 15H)
1.02 (s, 18H); 1.13 (s, 6H, 2J(Sn,H) 40.6); 1.44 (d, 3H, 3J(H,H) 6.5), 3.72 (d, 2H, 4J(H,H) 4.8, 3J(Sn,H) 49.4); 5.34 (m, 1H,
3J(Sn,H) 70.3); 6.93–7.36 (m, 15H)
21
22
0.99 (s, 6H, 2J(Sn,H) 56.2); 1.11 (s, 18H); 3.62 (s, 3H); 6.27 (s, 1H, 3J(Sn,H) 59.2); 6.63–7.34 (m, 20H)
0.84 (s, 6H, 2J(Sn,H) 49.7); 1.36 (s, 18H); 3.46 (s, 3H); 5.84 (s, 1H, 3J(Sn,H) 56.2); 6.63–7.34 (m, 20H)
In CDCl3; multiplicity and J values in parentheses; coupling constants in Hz; bs, broad singlet.

178
V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
[SnNeof2]+); 297 (13%, [M−Neof3]+, Sn-pattern); 253
(10%, [SnNeof]+); 197 (38%, Sn-pattern); 177 (10%,
[M−SnNeof3]+); 133 (6%, [Neof]+); 118 (5%, [Sn]+).
3.2. Addition of trineophyltin hydride (1) to substituted
alkynes catalyzed by bis(triphenylphosphine)
palladium(II) chloride
To a solution of methyl propiolate (0.15 g, 1.78 mmol)
and bis(triphenylphosphine) palladium(II) chloride
(0.025 g, 0.0358 mmol) in dry THF (5 ml) under nitrogen
was added 1 (0.924 g, 1.78 mmol), and the mixture was
stirred at r.t. during 30 min. The solvent was distilled off
under reduced pressure. The 119Sn-NMR spectrum
showed that under these conditions a mixture of two
compounds was formed: methyl (E)-3-(trineophylstan-
nyl)propenoate (5) (31%) and methyl 2-(trineophylstan-
nyl)propenoate (20) (69%). Flash chromatography (silica
gel 60) of the mixture afforded 5 (0.22 g, 0.37 mmol, 26%)
and 20 (0.49 g, 0.83 mmol, 56%), in the fractions eluted
with hexane/diethyl ether (85:15).
3.2.1.6. (Z)-2-trineophyltin-3-phenyl-2-propenol (7). MS
(m/z, relative intensity): 652 (M+; Sn-pattern); 519
(100%, [M−Neof]+, Sn-pattern); 402 (17%, Sn-pattern);
384 (13%, [M−Neof2]+, Sn-pattern); 253 (11%, [M−
Neof3]+, Sn-pattern); 197 (19%, Sn-pattern); 133 (10%,
[M−SnNeof3]+); 118 (3%, [Sn]+); 55 (11%, [C3H3O]+).
3.2.1.7. (Z)-3-trineophyltin-2-butenol (8). MS (m/z, rela-
tive intensity): 590 (M+; Sn-pattern); 519 (6%,
[SnNeof3]+); 457 (100%, [M−Neof]+, Sn-pattern); 443
(14%, Sn-pattern); 385 (11%, [SnNeof2]+); 324 (3%,
[M−Neof2]+, Sn-pattern); 253 (20%, [SnNeof]+) 197
(25%, Sn-pattern); 191 (10%, [M−Neof3]+, Sn-pattern);
133 (5%, [Neof]+); 118 (2%, [Sn]+); 105 (10%, [C8H9]+);
55 (26%, [C3H3O]+).
3.2.1. Mass spectra of the new 6inyltin compounds
3.2.1.1. (E)-trineophyltinphenylethylene (2). MS (m/z,
relative intensity): 622 (M+, Sn-pattern); 519 (4%,
[SnNeof3]+); 489 (100%, [M−Neof]+, Sn-pattern); 464
(8%, Sn-pattern); 431 (4%, Sn-pattern); 423 (2%, Sn-pat-
tern); 385 (1%, [SnNeof2]+); 375 (5%, Sn-pattern); 355
(2%, [M−Neof2]+, Sn-pattern); 253 (4%, [SnNeof]+);
223 (10%, [M−Neof3]+, Sn-pattern); 197 (12%, Sn-pat-
tern); 105 (9%, [M−SnNeof3]+); 118 (6%, [Sn]+).
3.2.1.8. (Z)-2-trineophyltin-2-butenol (9). MS (m/z, rela-
tive intensity): 590 (M+; Sn-pattern); 519 (7%,
[SnNeof3]+); 457 (100%, [M−Neof]+, Sn-pattern); 443
(13%, Sn-pattern); 385 (11%, [SnNeof2]+); 324 (2%,
[M−Neof2]+, Sn-pattern); 253 (15%, [SnNeof]+); 197
(27%, Sn-pattern); 191 (9%, [M−Neof3]+, Sn-pattern);
133 (6%, [Neof]+); 118 (4%, [Sn]+); 105 (11%, [C8H9]+);
55 (31%, [C3H3O]+).
3.2.1.2. (Z)-3-trineophyltin-2-propenol (3). MS (m/z, rel-
ative intensity): 576 (M+; Sn-pattern); 519 (13%,
[SnNeof3]+); 443 (100%, [M−Neof]+, Sn-pattern); 403
(20%, Sn-pattern); 385 (17%, [SnNeof2]+); 253 (15%,
[SnNeof]+); 197 (30%, Sn-pattern); 177 (5%, [M−
Neof3]+, Sn-pattern); 133 (10%, [Neof]+); 118 (3%,
[Sn]+); 57 (3%, [M−SnNeof3]+).
3.2.1.9. (Z)-3-trineophyltin-3-phenyl-2-propenoic acid
methyl ester (10). MS (m/z, relative intensity): 680 (M+;
Sn-pattern); 547 (100%, [M−Neof]+, Sn-pattern); 519
(71%, [SnNeof3]+); 415 (3%, [M−Neof2]+, Sn-pattern);
385 (5%, [SnNeof2]+); 281 (18%, [M−Neof3]+, Sn-pat-
tern); 253 (10%, [SnNeof]+); 197 (30%, Sn-pattern); 149
(7%, Sn-pattern); 133 (8%, [Neof]+); 118 (3%, [Sn]+); 105
(8%, [C8H9]+).
3.2.1.3. (Z)-3-trineophyltin-2-propenoic acid methyl ester
(4). MS (m/z, relative intensity): 604 (M+; Sn-pattern);
519 (10%, [SnNeof3]+); 471 (100%, [M−Neof]+, Sn-pat-
tern); 385 (3%, [SnNeof2]+); 338 (4%, [M−Neof2]+,
Sn-pattern); 253 (14%, [SnNeof]+); 205 (9%, [M−
Neof3]+, Sn-pattern); 133 (7%, [Neof]+); 118 (5%, [Sn]+).
3.2.1.10. (E)-2-trineophyltin-maleic acid dimethyl ester
(11). MS (m/z, relative intensity): 662 (M+; Sn-pattern);
529 (100%, [M−Neof]+, Sn-pattern); 519 (40%,
[SnNeof3]+); 396 (4%, [M−Neof2]+, Sn-pattern); 385
(2%, [SnNeof2]+); 277 (6%, [M−SnNeof2]+); 263 (20%,
[M−Neof3]+, Sn-pattern); 197 (20%, Sn-pattern); 143
(20%, [M−SnNeof3]+); 133 (10%, [Neof]+); 118 (3%,
[Sn]+).
3.2.1.4. (E)-3-trineophyltin-2-propenoic acid methyl ester
(5). MS (m/z, relative intensity): 604 (M+; Sn-pattern);
519 (11%, [SnNeof3]+); 471 (100%, [M−Neof]+, Sn-pat-
tern); 385 (5%, [SnNeof2]+); 338 (3%, [M−Neof2]+,
Sn-pattern); 253 (15%, [SnNeof]+); 205 (10%, [M−
Neof3]+, Sn-pattern); 133 (7%, [Neof]+); 118 (4%, [Sn]+).
3.2.1.11. 1-Trineophyltin-1-phenylethylene (12). MS (m/
z, relative intensity): 622 (M+; Sn-pattern); 519 (2%,
[SnNeof3]+); 489 (100%, [M−Neof]+, Sn-pattern); 464
(9%, Sn-pattern); 433 (3%, Sn-pattern); 421 (1%, Sn-pat-
tern); 385 (1%, [SnNeof2]+); 377 (3%, Sn-pattern); 355
(1%, [M−Neof2]+, Sn-pattern); 253 (4%, [SnNeof]+);
223 (14%, [M−Neof3]+, Sn-pattern); 197 (15%, Sn-pat-
tern); 118 (5%, [Sn]+); 103 (9%, [M−SnNeof3]+).
3.2.1.5. (Z)-trineophyltin-1,2-diphenylethylene (6). MS
(m/z, relative intensity): 696 (M+; Sn-pattern); 565
(100%, [M−Neof]+, Sn-pattern); 519 (35%, [SnNeof3]+);
431 (2%, [M−Neof2]+, Sn-pattern); 385 (2%,

V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
179
3.2.1.12. (E)-3-trineophyltin–2-propenol (13). MS (m/z,
relative intensity): 576 (M+; Sn-pattern); 519 (7%,
[SnNeof3]+); 443 (100%, [M−Neof]+, Sn-pattern); 403
(22%, Sn-pattern); 385 (19%, [SnNeof2]+); 253 (15%,
[SnNeof]+); 197 (31%, Sn-pattern); 177 (5%, [M−
Neof3]+, Sn-pattern); 133 (13%, [Neof]+); 117 (5%,
[Sn]+); 57 (1%, [M−SnNeof3]).
3.2.1.19. 2-Trineophyltin-2-propenoic acid methyl ester
(20). MS (m/z, relative intensity): 604 (M+; Sn-pat-
tern);519 (62%, [SnNeof3]+); 471 (100%, [M−Neof]+,
Sn-pattern); 385 (3%, [SnNeof2]+); 338 (3%, [M−
Neof2]+, Sn-pattern); 253 (12%, [SnNeof]+); 205 (2%,
[M−Neof3]+, Sn-pattern); 133 (8%, [Neof]+); 118 (4%,
[Sn]+).
3.2.1.13. 2-Trineophyltin–2-propenol (14). MS (m/z, rel-
ative intensity): 576 (M+; Sn-pattern); 519 (11%,
[SnNeof3]+); 443 (100%, [M−Neof]+, Sn-pattern); 403
(20%, Sn-pattern); 385 (17%, [SnNeof2]+); 253 (13%,
[SnNeof]+); 197 (34%, Sn-pattern); 177 (7%, [M−
Neof3]+, Sn-pattern); 133 (12%, [Neof]+); 118 (4%,
[Sn]+); 57 (2%, [M−SnNeof3]+).
3.2.1.20. (E)-3-trineophyltin-3-phenyl-2-propenoic acid
methyl ester (21). MS (m/z, relative intensity): 680 (M+;
Sn-pattern); 547 (62%, [M−Neof]+, Sn-pattern); 519
(5%, [SnNeof3]+); 415 (11%, [M−Neof2]+, Sn-pat-
tern); 385 (29%, [SnNeof2]+); 281 (6%, [M−Neof3]+,
Sn-pattern); 253 (10%, [SnNeof]+); 197 (21%, Sn-pat-
tern); 149 (13%, Sn-pattern); 133 (14%, [Neof]+); 118
(6%, [Sn]+); 105 (11%, [C8H9]+).
3.2.1.14. (E)-trineophyltin-1,2-diphenylethylene (15). MS
(m/z, relative intensity): 696 (M+; Sn-pattern); 565
3.2.1.21. (E)-2-trineophyltin-3-phenyl-2-propenoic acid
methyl ester (22). MS (m/z, relative intensity): 680 (M+;
Sn-pattern); 547 (100%, [M−Neof]+, Sn-pattern); 519
(73%, [SnNeof3]+); 415 (2%, [M−Neof2]+, Sn-pat-
tern); 385 (4%, [SnNeof2]+); 281 (17%, [M−Neof3]+,
Sn-pattern); 253 (11%, [SnNeof]+); 197 (29%, Sn-pat-
tern); 149 (9%, Sn-pattern); 133 (9%, [Neof]+); 118 (3%,
[Sn]+); 105 (9%, [C8H9]+).
(100%,
[M−Neof]+,
Sn-pattern);
519
(38%,
[SnNeof3]+); 431 (1%, [M−Neof2]+, Sn-pattern); 385
(1%, [SnNeof2]+); 297 (15%, [M−Neof3]+, Sn-pat-
tern); 253 (9%, [SnNeof]+); 197 (41%, Sn-pattern); 177
(13%, [M−SnNeof3]+); 133 (7%, [Neof]+); 118 (4%,
[Sn]+).
3.2.1.15. (E)-2-trineophyltin-3-phenyl-2-propenol (16).
MS (m/z, relative intensity): 652 (M+; Sn-pattern); 519
(100%, [M−Neof]+, Sn-pattern); 463 (9%, Sn-pattern);
421 (5%, Sn-pattern); 405 (1%, Sn-pattern); 387 (2%,
[M−Neof2]+, Sn-pattern); 351 (1%, Sn-pattern); 329
(1%, Sn-pattern); 275 (3%, Sn-pattern); 253 (11%,
[SnNeof3]+); 235 (6%, Sn-pattern); 197 (25%, Sn-pat-
tern); 133 (24%, [M−SnNeof3]+); 119 (5%, [Sn]+); 55
(29%, [C3H3O]+).
Acknowledgements
This work was supported by grants from CONICET
(Capital Federal, Argentina) and Universidad Nacional
del Sur (Bah´ıa Blanca, Argentina). The generous help
of Professor M. Gonza´lez Sierra (IQUIOS, Rosario,
Argentina) and Professor T.N. Mitchell and P. Urschel
(Dortmund University, Dortmund, Germany) in ob-
taining the NMR spectra and Mass spectra is acknowl-
edged. A travel grant to one of us (JCP) from the
Alexander von Humboldt Foundation, and a fellowship
from CONICET and at present from DAAD (Ger-
many) to VID are also gratefully acknowledged.
3.2.1.16. (E)-3-trineophyltin-3-phenyl-2-propenol (17).
MS (m/z, relative intensity): 652 (M+; Sn-pattern); 519
(52%, [M−Neof]+, Sn-pattern); 403 (34%, Sn-pattern);
385 (15%, [M−Neof2]+, Sn-pattern); 253 (13%, [M−
Neof3]+, Sn-pattern); 197 (25%, Sn-pattern); 133 (14%,
[M−SnNeof3]+); 117 (7%, [Sn]+); 55 (20%, [C3H3O]+).
3.2.1.17. (E)-2-trineophyltin-2-butenol (18). MS (m/z,
relative intensity): 590 (M+; Sn-pattern); 519 (6%,
[SnNeof3]+); 457 (100%, [M−Neof]+, Sn-pattern); 443
(14%, Sn-pattern); 324 (4%, [M−Neof2]+, Sn-pattern);
253 (23%, [SnNeof]+); 197 (25%, Sn-pattern); 191 (12%,
[M−Neof3]+, Sn-pattern); 133 (7%, [Neof]+); 118 (4%,
[Sn]+); 105 (9%, [C8H9]+); 55 (15%, [C3H3O]+).
References
[1] (a) M. Pereyre, J.-P. Quintard, A. Rahm, Tin in Organic Synthe-
sis, Butterworths, London, 1987;
(b) N.D. Smith, J. Mancuso, M. Lautens, Chem. Rev. 100 (2000)
3257;
(c) A. Barbero, F.J. Pulido, J.A. Rinco´n, P. Cuadrado, D. Galis-
teo, H. Mart´ınez-Garc´ıa, Angew. Chem. Int. Ed. 40 (2001) 2101.
[2] (a) S. Usugi, J. Tang, H. Shinokubo, K. Oshima, Synlett (1999)
1417;
3.2.1.18. (E)-3-trineophyltin-2-butenol (19). MS (m/z,
relative intensity): 590 (M+; Sn-pattern); 519 (7%,
[SnNeof3]+); 457 (100%, [M−Neof]+, Sn-pattern); 401
(3%, Sn-pattern); 385 (2%, [SnNeof2]+); 345 (3%, Sn-
pattern); 253 (4%, [SnNeof]+); 197 (14%, Sn-pattern);
133 (5%, [Neof]+); 118 (2%, [Sn]+); 55 (8%, [C3H3O]+).
(b) M. Alami, F. Ferri, Synlett (1996) 755;
(c) J.-F. Betzer, F. Delaloge, B. Muller, A. Pancrazi, J. Org.
Chem. 62 (1997) 7768.
[3] (a) A.B. Chopa, A.E. Zu´n˜iga, J.C. Podesta´, J. Chem. Research (S)
(1989) 234;

180
V.I. Dodero et al. / Journal of Organometallic Chemistry 650 (2002) 173–180
(b) J.C. Podesta´, N.N. Giagante, A.E. Zu´n˜iga, G.O. Danelon, O.A. [4] A.J. Leusink, H.A. Budding, W. Drenth, J. Organomet. Chem. 11
Mascaretti, J. Org. Chem. 59 (1995) 3747;
(c) J.C. Podesta´, A.B. Chopa, N.N. Giagante, A.E. Zu´n˜iga, J.
Organomet. Chem. 494 (1995) 5;
(d) J.C. Podesta´, A.B. Chopa, G.E. Radivoy, C.A. Vitale, J.
Organomet. Chem. 494 (1995) 11;
(1968) 541.
[5] F. Liron, P. Le Garrec, M. Alami, Synlett (1999) 246.
[6] A. Cope, M. Burg, J. Am. Chem. Soc. 74 (1952) 168.
[7] A.B. Chopa, A.E. Zu´n˜iga, J.C. Podesta´, J. Chem. Res. (S), (1989)
234.
(e) C.A. Vitale, J.C. Podesta´, J. Chem. Soc. Perkin Trans. 1 (1996)
2407.
[8] E.H. Huntress, T.E. Lesslie, J. Bornstein, Org. Synth. 32 (1952) 55.
[9] E.B. Bates, E.R.H. Jones, M.C. Whiting, J. Chem. Soc. (1954) 1854.