Synthesis, characterization and primary evaluation of the synthetic efficiency of supported vinyltins and allyltins

Article abstract of DOI:10.1016/j.jorganchem.2010.01.038

Supported vinyltins and allyltins grafted to an insoluble cross-linked polystyrene matrix were prepared using methods usually employed in solution, like hydrostannylation of alkynes, transmetallation of a tin halide with organomagnesium or organozinc reagents, and substitution of an allyl halide by a supported stannylanion or S_N2′ substitution of a supported β-stannylacrolein acetal by cyanocopper reagents in the presence of boron trifluoride etherate. The insoluble grafted organotin reagents were analysed by HRMAS NMR, allowing an unambiguous assignment of their isomeric distribution or the identification of side products. When involved in Stille cross-coupling reactions (vinyltins) or in addition on aldehydes (allyltins), these supported reagents exhibit similar reactivity and similar stereoselectivity when compared to the tributyltin analogues, with the advantage to prevent problems due to the contamination by tin residues.

Full text of DOI:10.1016/j.jorganchem.2010.01.038

Journal of Organometallic Chemistry 695 (2010) 1414–1424
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, characterization and primary evaluation of the synthetic efficiency
of supported vinyltins and allyltins
Gaelle Kerric a, Erwan Le Grognec a, Valérie Fargeas a, Françoise Zammattio a, Jean-Paul Quintard a,
,
*
Monique Biesemans b, Rudolph Willem b,
*
a Université de Nantes, CNRS, Chimie Et Interdisciplinarité: Synthèse, Analyse et Modélisation (CEISAM), UMR CNRS 6230, Faculté des Sciences et des Techniques;
2, rue de la Houssinière, BP 92208, F-44322 Nantes Cedex 3, France
b Vrije Universiteit Brussel, High Resolution NMR Centre, Pleinlaan 2, B-1050 Brussel, Belgium
a r t i c l e i n f o
a b s t r a c t
Article history:
Supported vinyltins and allyltins grafted to an insoluble cross-linked polystyrene matrix were prepared
using methods usually employed in solution, like hydrostannylation of alkynes, transmetallation of a tin
halide with organomagnesium or organozinc reagents, and substitution of an allyl halide by a supported
stannylanion or SN20 substitution of a supported b-stannylacrolein acetal by cyanocopper reagents in the
presence of boron trifluoride etherate. The insoluble grafted organotin reagents were analysed by HRMAS
NMR, allowing an unambiguous assignment of their isomeric distribution or the identification of side
products. When involved in Stille cross-coupling reactions (vinyltins) or in addition on aldehydes (allyl-
tins), these supported reagents exhibit similar reactivity and similar stereoselectivity when compared to
the tributyltin analogues, with the advantage to prevent problems due to the contamination by tin
residues.
Received 9 December 2009
Received in revised form 27 January 2010
Accepted 28 January 2010
Available online 4 February 2010
Keywords:
Vinyltin
Allyltin
HRMAS NMR
Stille
Ó 2010 Elsevier B.V. All rights reserved.
Allylstannation
1. Introduction
ported N-stannylanilines to obtain regioselective para-iodination
[8] and, even more interestingly, we have used supported allyltins
Triorganotin compounds are welcomed as powerful reagents in
organic synthesis due to their versatile reactivity and high toler-
ance against numerous functional groups [1]. For instance, vinyl-
tins have been used as irreplaceable reagents in the total
in order to obtain cleanly homoallyllic alcohols [9] or supported
vinyltins and aryltins to achieve Stille-Migita cross-coupling reac-
tions [10,11], a topic which remains of high interest as illustrated
by reports from other groups [12–14]. High Resolution Magic Angle
Spinning NMR (HRMAS NMR) [6] enables one to monitor more effi-
ciently supported organotin reagents in order to exploit further
their synthetic potential in novel solid phase synthetic procedures.
The present contribution reports on the synthesis, the character-
ization and the reactivity of vinyltins and allyltins grafted onto a
solid support of polystyrene cross-linked divinylbenzene (Amber-
lite XE 305). The choice of the latter support has been dictated
by the mechanical resistance of the polymer to abrasion, the size
of the pores and the ability of this cross-linked material to swell
optimally in usual organic solvents [15], which is a prerequisite
to both favourable reaction and HRMAS NMR measurement condi-
tions. As previously described [5,8] a grafted n-butyl group was
used as a spacer for a di-n-butyltin unit in order to preserve a per-
fect analogy with the tri-n-butyltin analogues (Scheme 1).
The obtained supported triorganotin halides 3a–c can be subse-
quently converted into supported triorganotin hydride 4 upon
reaction with LiAlH4 [10] or reacted with Grignard reagents or zinc
reagents [9], affording a series of grafted allyltins, vinyltins and
aryltins [9–11].
synthesis of complex molecules [2] and
c-substituted allyltins
have been used in the stereocontrolled synthesis of homoallylic
alcohols [3]. In spite of their synthetic potential, these reagents
have been scarcely used for the synthesis of bioactive molecules
like pharmaceuticals because of their toxicity and the difficulty
to remove tin by-products from the desired reaction products. Sev-
eral possibilities have been disclosed to alleviate this issue and
have been recently reviewed [4]. Among these, using insoluble so-
lid-state supported organotin reagents appears to be the most
promising approach because the grafted organotin residues can
be efficiently removed by simple filtration of the solid support to
which they are grafted. Pioneering studies have been devoted
to supported organotin hydrides in reduction reactions [5] and
to supported organotin oxides used as transesterification catalysts
[6,7]. More recently, we have pointed out the efficiency of sup-
* Corresponding authors. Tel.: +33 251 12 54 08; fax: +33 251 12 54 02.
E-mail addresses: jean-paul.quintard@univ-nantes.fr (J.-P. Quintard), rwillem@
vub.ac.be (R. Willem).
0022-328X/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.01.038

G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
1415
Scheme 1. Grafting of organotin reagents on Amberlite XE 305. Reagents and conditions: (a) n-BuLi/TMEDA, cyclohexane, 65 °C. (b) Br–(CH2)4–Cl, THF, 0 °C to rt. (c)
Bu2SnPhLi, THF, rt. (d) I2, EtOH, 65 °C; Br2, EtOH, 65 °C or HCl, Et2O/THF, 20 °C.
the 13C spectrum, three resonances, representative for the three
2. Results
isomers present, are observed for several carbon atoms. The spec-
trum was simulated with the PERCH programme [22,23] in order
to determine the relative amplitudes of each of the three reso-
nances of a given carbon atom type, which turned out to be 17–
72–11% for the vinyl resonances, 12–76–12% for the CH(OEt)2 ones,
14–71–15% for OCH2 ones and 13–73–14% for SnCH2 signals. These
relative amplitudes, averaging at 14.0 2.2, 73.0 2.2, 13.0 1.8%,
respectively, are in the same range for all sets of three 13C reso-
nances within experimental error and are therefore representative
for the percentage molar fractions of the three isomers. In order to
address the assignment issue, the synthesis of pure isomer 5b-Z
was attempted, starting from 3c according to the procedure used
in tributyltin series (Scheme 3) [24].
While 6 was correctly obtained, the subsequent Sato type reac-
tion failed when performed on the supported alkynyltin 6, probably
because adding the reagents in the same order as in homogeneous
liquid phase is not possible. Indeed, the dropwise addition of the
grafted alkynyltin 6 to Ti(OiPr)4 prior to treatment with isopropyl-
magnesium chloride (2 equiv.) [24] is simply not applicable.
The second target was pure vinyltin 5a and for this purpose 2-
lithioacrolein acetal obtained by halogen/metal exchange with the
corresponding bromoacetal was reacted with the supported trior-
ganotin iodide 3c (Scheme 4).
2.1. Synthesis and structural analysis of isomeric mixtures of
supported vinyltins
When functional groups have to be preserved on the vinyl unit,
hydrostannation of the appropriate alkyne is the straightforward
route. Accordingly, we focused on the reaction of propargyl or
homopropargyl acetals with the supported tin hydride
(Scheme 2) [16–18].
4
While characterization of supported organotin reagents can be
achieved using solid-state 119Sn MAS NMR, in the present case,
the signal of 5a is overlapping with the one of 5b-E preventing
complete discrimination between the three isomers. The iododest-
annylation, known to be quantitative [16], has been used as an
indirect method to evaluate broadly the ratio of 5a/5b-E/5b-Z to
be 13/73/14, but this method is questionable on more complex
examples. Accordingly, the isomeric mixture composition was
investigated using HRMAS NMR, allowing the application of typical
high-resolution liquid NMR techniques to solid supported grafted
moieties dipped in the liquid [19–21], thanks to their isotropic con-
formational mobility characteristic to the liquid state. However, as
in the solid-state 119Sn MAS spectrum, the resonances of 5a and
5b-E also overlap in the 119Sn HRMAS spectrum. By contrast, in
Scheme 2. Preparation of supported vinyltins via hydrostannylation of alkynes. Reagents and conditions: (a) LiAlH4 THF, 60 °C, 3 h. (b) AIBN, 3,3-diethoxypropyne, toluene,
110 °C, 3 h.
Scheme 3. Attempted synthesis of supported vinyltin 5b-Z. Reagents and conditions: (a) n-BuLi, THF, ꢀ78 °C. (b) 3c. (c) Ti(OiPr)4, i-PrMgCl (2 equiv.), Et2O, ꢀ78 °C.
Scheme 4. Synthesis of branched supported organotin 5a.

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G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
Fig. 1. Expansions of 13C spectra of the mixture of the three isomers (5a + 5b-E + 5b-Z) (bottom) and 5a (top) (5a is contaminated with 6).
Unfortunately,
a
competitive dehydrobromination occurred
tion in the tributyltin series; a similar trend is observed for the
supported tin hydride affording a Z/E mixture of the supported
vinyltin 7 (Scheme 5).
during the halogen metal exchange reaction, affording diet-
hoxypropyne which was converted into the corresponding
alkynyllithium to afford 6 after quenching with the supported tin
halide (see the first step of Scheme 3). In spite of the formation
of side-product 6 an unambiguous discrimination of the relevant
signals related to the different isomers in the 13C HRMAS spectrum
was now possible, as in three of the previously mentioned sets of
differentiated carbon atoms the resonances of 5a could formally
be identified (Fig. 1).
The generation of a 74/26 mixture of E/Z isomers was easily
established from the solid-state 119Sn MAS NMR spectrum due to
the similarity of the 119Sn chemical shifts with those of the soluble
tributyltin derivatives, and the HRMAS NMR spectra enabled us to
complete the 1H and 13C resonance assignment of the vinyl part.
Although the resonances are broad in the 1H HRMAS spectrum
and, as a consequence no reliable relation exists between the iso-
mer concentrations and their relative resonance amplitudes, the
13C NMR data confirm the presence of an excess of E isomer thanks
The full assignment of the 1H resonances could be completed
thanks to 1H/13C HSQC and 1H/119Sn HMQC [21] spectra and the re-
sults are provided in the experimental part (Table 1). In order to as-
sess the potentials of the method on another structure, where the
vinylic protons have very close chemical shifts for the E isomer, the
supported homoallyl vinyltin acetals 7 were synthesized similarly.
In this series, the a-isomer was not observed after hydrostannyla-
Table 1
1H, 13C and 119Sn chemical shifts in CDCl3 of the grafted parts of 5a and 5b-(E/Z).
Moiety
Vinyl 1
d
13C
d 1H
d
119Sn
144.9 (5b-E)
6.08 (5b-E)
5.94 (5a)
6.24 (5b-Z)
6.02 (5b-Z)
6.41 (5b-E)
5.43 (5a)
Vinyl 2
134.0
132.5 (5b-E)
131.2
CH(OEt)2 107.4 (5a)
103.0 (5b-E)
4.78 (5a)
4.84 (5b-E)
4.87 (5b-Z)
3.66, 3.53
101.9 (5b-Z)
OCH2
61.2 (5a)
60.8 (5b-E)
60.2 (5b-Z)
OCH2CH3 15.3
1.24
0.92
Butyl
a
10.9 (5a)
10.0 (5b-Z)
9.5 [335](5b-E)
29.1
Butyl b
Butyl
1.55
1.35
0.92
c
27.2
Butyl d
13.7
Fig. 2. Expansion of the 1H/13C HSQC HRMAS spectrum of 7-E/Z with the 1H and 13
C
Sn
ꢀ46.6 (13% 5a + 73% 5b-E),ꢀ60.6
(14% 5b-Z)
HRMAS spectra on the horizontal and vertical axes respectively. The relevant 13C
allylic resonances are indicated.
Scheme 5. Synthesis of supported homoallyl vinyltin acetals 7-E and 7-Z. Reagents and conditions: (a) AIBN, 4,4-diethoxybut-1-yne, toluene, 110 °C, 3 h.

G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
1417
Table 2
1H, 13C and 119Sn chemical shifts in C6D6 of the grafted parts of 7-(E/Z).
Atom
d
13C
d
1H
d
119Sn
Vinyl 1
Vinyl 2
CH(OEt)2
OCH2
145.5
130.9
102.9
61.3
6.32
6.30
4.73
3.74, 3.57
1.31
OCH2CH3
15.8
C@CꢀCH2 45.2 (E); 43.0 (Z) 3.32 (E); 2.78 (Z)
Butyl
Butyl b
Butyl
a
10.0
29.6
27.9
14.3
1.17
1.79
1.55
1.11
c
Butyl d
Sn
ꢀ51.9 (79%); ꢀ62.3 (21%)
Fig. 3. 119Sn HR-MAS spectra of supported crotyltins 9. Bottom: spectrum of the
Barbier reaction mixture; top: spectrum of the mixture obtained after quenching of
the stannylanion.
to the possible spectral discrimination of the allylic 13C
(ꢀC@CꢀCH2) resonances from the Z and E isomers, at 43.0 and
45.2 ppm, respectively. Further analysis involving a 1H/13C HSQC
experiment (Fig. 2) makes a complete assignment possible (see
Table 2).
The NMR studies of the crotyltin series in CDCl3 reveal a partial
halodestannylation. In this solvent, the 119Sn NMR spectrum exhib-
its an additional resonance at +150 ppm assigned to the supported
triorganotin chloride 3a and therefore, spectra must be preferably
recorded in C6D6 to avoid this side-problem.
2.2. Synthesis and structural analysis of supported isomeric mixtures
of allyltins
2.2.1. Supported crotyltins
The assignment of the E/Z configuration of compound 9 was
performed by comparison with the spectra of the soluble model
compounds, E/Z-(2-butenyl)tributylstannane. Although these
products were described several years ago [26], divergent assign-
ments have been published because no complete NMR character-
ization had been performed so far. Therefore an elaborate study
including 1D 1H, 13C, 119Sn and 2D 1H–1H, 1H–13C and 1H–119Sn
correlation NMR spectra was performed and the results are gath-
ered in Table 4. A 1H–1H NOESY spectrum, revealing a correlation
peak between the resonances from the SnCH2 and the vinylic pro-
tons in position 3, confirmed the E configuration of the major com-
pound in the mixture of the soluble model compounds, which was
prepared according to the Barbier type reaction from E/Z crotyl
chloride (85/15). The grafted compounds show an excess of Z-iso-
mer in both preparations.
Even though, quite surprising at first glance, this result can be
understood as a difference in kinetics of the 1,3-metallotropy
inducing an isomerisation process and/or by a matrix effect favour-
ing the Z-isomer Scheme 7.
The difference in the distribution of product 9ꢀ(Z+E) and 10 as a
function of the experimental procedure can also be interpreted by
a thermodynamic mixture of isomers when preparation is achieved
in Barbier mode, while a mixture not yet at equilibrium can be ex-
pected using the stannylanion 8, because triorganostannyllithium
Differences in reactivity of supported crotyltins toward benzal-
dehyde were observed when compared to crotyltributyltin, due to
a matrix effect on the kinetics of 1,3-metallotropy [25]. HRMAS
NMR techniques enable one to estimate semi-quantitatively the
differences in isomeric composition of the supported reagents as
a function of their preparation method. Two samples were ob-
tained from crotyl chloride through two different procedures
(Scheme 6). A supported stannylanion has been generated here
in situ for the first time: the compatibility of cross-linked sty-
rene/divinylbenzene matrix (Amberlite XE 305) with THF gives ac-
cess to the supported triorganostannyllithium reagent 8 from the
tin hydride 4.
Whereas the solid-state 119Sn MAS spectra of the two samples
resulting from a Barbier reaction or from the quenching of the
intermediate supported stannylanion 8 are quite similar, the corre-
sponding 119Sn HRMAS spectra enable one to unravel the outcome
of these reactions (Fig. 3). The latter reaction mixture shows the
presence of a third isomer, with a slightly different 119Sn chemical
shift, assigned to the branched isomer 10 from its 2D 1H-119Sn
HSQC HRMAS NMR spectrum (Fig. 4), in which all 119Sn resonances
clearly display cross-peaks with the
a and b proton resonances
from the butyl groups, the SnꢀCH–Me proton and with the vinylic
protons. A complete assignment for the three isomers is provided
in Table 3.
*
Scheme 6. Synthesis of supported crotyltins 9-(E and Z) and 10. Reagents and conditions: (a) Zn , crotylchloride (E/Z = 85/15), Barbier method, (b) LiAlH4, THF, 60 °C, 3 h. (c) i-
Pr2NLi, THF, ꢀ10 °C. (d) Crotylchloride (E/Z = 85/15).

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G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
Fig. 4. Part of the 1H/119Sn HSQC HRMAS NMR spectrum of the mixture 9-Z, 9-E and 10 obtained after quenching of the stannylanion.
Table 3
1H, 13C and 119Sn chemical shifts in C6D6 of the grafted parts of 9-(Z/E) and 10. The first value concerns the major isomer, with Z-configuration.
Bu
Bu
Bu
Bu
Bu
1
Bu
1
δ
β
δ
β
2
4
2
Sn
Sn
Sn
3
4
γ
γ
α
3
α
9-E
9-Z
10
9-(Z/E)
d
13C
d
1H
d
119Sn
10
d
1H
d
119Sn
Butyl
Butyl b
Butyl
Butyl d
a
9.8/9.6
1.07
Butyl
Butyl b
a
1.00
1.71
29.7/28.7
27.9/27.2
14.1
1.71/1.75
1.50/1.43
1.07
c
Butenyl 1
Butenyl 2
Butenyl 3
Butenyl 4
10.6/14.7
1.96/1.94
5.85/5.78
5.42/5.45
1.77/1.81
Butenyl CH
Butenyl CH@
2.35
4.98
129.5/130.5
118.4/120.5
12.9/18.3
Butenyl CH3
1.51
Sn in mixture (Barbier)
ꢀ14.0 (Z 64%)
ꢀ18.0 (E 36%)
ꢀ14.0 (Z 66%)
ꢀ18.0 (E 26%)
Sn in mixture (stannylanion)
ꢀ17.1 (8%)
Table 4
1H, 13C and 119Sn chemical shifts in C6D6 of a mixture of E/Z 2-butenyl tri-n-butyltin (for numbering scheme see Table 3). nJ(13C/119/117Sn) coupling constants in Hz are mentioned
between brackets.
Major (E)
13C
Minor (Z)
13C
Atom
Butyl
Butyl b
Butyl
d
d
1H
d
119Sn
d
d
1H
d
119Sn
a
9.4 [313/299]
29.6 [19.8]
27.7 [51.2]
13.9
14.5 [267/256]
130.4 [44.3]
120.4 [46.8]
18.1 [11.6]
0.91
1.55
1.34
0.92
1.79
5.65
5.32
1.67
9.6 [313/299]
29.6 [19.8]
27.8 [53.3]
13.8
10.4 [255/245]
129.5 [44.7]
118.3 [45.4]
12.7 [13.0]
0.91
1.54
1.35
0.86
1.82
5.72
5.29
1.63
c
Butyl d
Butenyl 1 (CH2)
Butenyl 2
Butenyl 3
Butenyl 4 (CH3)
Sn
ꢀ19.2 (57%)
ꢀ15.0 (43%)

G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
1419
LA or Bu3Sn
LA or Bu3Sn
Me
SnBu3
Me
SnBu3
Bu3Sn
Me
10
9-E
9-Z
Scheme 7. Isomerisation of crotyltins.
Table 6
has been described to react primary with allyl chlorides [27] and
tosylates [28] through an SN2 pathway, the partial isomerisation
occurring subsequently depending on the substrates and on the
experimental conditions.
1H, 13C and 119Sn meaningful chemical shifts in CDCl3 of the grafted parts of 11c and
11d. The values between brackets are the 1H chemical shifts in C6D6.
Atom
d
13C
d
1H
d
119Sn
11c
11d
11c
11d
11c
11d
Vinyl 1
Vinyl 2
OCH2
OCH2CH3
C@C–CH
C(CH3)3
CH(CH3)2
CH(CH3)2
141.0
109.4
67.2
141.3
108.4
67.2
15.4
39.9
30.7
5.82
4.46
3.72
5.83 (5.93)
4.50 (4.72)
3.72 (3.66)
1.30
2.63 (3.02)
0.98
2.2.2. Supported
a
-substituted
c
-alkoxyallyltins
In the tributyltin series,
a
-substituted -alkoxyallyltins were
c
obtained from acrolein b-tributylstannylacetals through a SN20
reaction [29,30]; therefore, a similar reaction for the supported
analogues 5b-E and 5b-Z according to Scheme 8, was expected,
see Table 5.
15.4
2.48
1.94
13.8?
Butyl
Butyl b
Butyl
Butyl d
Sn
a
9.9
10.8
29.3
27.7
13.8
0.93
1.54
1.36
0.93
0.94
1.54
1.36
0.92
In practice, using tributyltin reagents [29,30] for the synthesis
of supported allyltins appears to be much less efficient. For in-
stance, using MeCu(CN)Li and LiBr in diethyl ether or THF, the
SN20 reaction product 11a could not be obtained, whatever the
reaction conditions. When the reaction was attempted with Et-
Cu(CN)MgCl in diethyl ether, the desired product 11b was obtained
in 32% yield, and with i-PrCu(CN)MgCl, allyltin 11c was obtained
with 47% yield, using THF as a solvent. Surprisingly, when at-
tempted with a t-butyl copper reagent, the reaction works in
diethyl ether but only when a 2/1 ratio of t-BuMgCl/CuCN was
used, 11d being likewise obtained in 47% yield. In every case,
side-products such as supported triorganotin chloride 3a or sup-
ported tetraorganotins (transmetallation products) were observed.
Obviously this reaction is far from being optimal and some dis-
crepancies in the reactivity might be due to differences in the
aggregation state of the organocopper reagent, which is believed
to be higher with MeCu(CN)Li or Me2Cu(CN)Li2, because of the
incorporation of LiBr into the structure of the organometallic re-
agent [31] or to other problems related to the organocopper struc-
ture [32].
29.3
27.6
13.8
c
ꢀ25.6
ꢀ29.8
the allyl moiety at 5.83, 4.50 and 3.72 ppm. According to informa-
tion from soluble model compounds formal indicators of the con-
figuration around the double bond are the 1H chemical shifts of
the vinylic protons, which resonate at lower frequency and display
a larger
Dd for the Z-configuration. The values 5.83, 4.50 and
3.72 ppm are in accordance with those found for the Z-configura-
tion of Bu3SnCH(t-Bu)CH@CHꢀOEt, reported as 5.74, 4.39 and
3.65 ppm, whereas those of the E-configuration resonate at 6.05,
4.88 and 3.45 ppm. [30] Further confirmation of the Z-configura-
tion for this compound can be gathered from a 1H–1H NOESY
experiment (Fig. 5), in which only one of the vinylic protons, i.e.
the one at 5.83 ppm assigned to the proton on the same carbon
atom as the ethoxy group, displays a correlation peak with the
OCH2 protons of the ethoxy group. For the E-configuration, correla-
tion peaks with both the vinylic protons are to be expected. These
observations allow the assignment of a Z-configuration for the ma-
jor isomer in each case, in agreement with previous observations
on tributyltin derivatives [29]. The sample with the isopropyl
In spite of these poor yields, compounds 11c and 11d have been
characterized from 2D 1H HRMAS correlation spectra. Full chemical
shift data for the
a-t-butyl-substituted c-ethoxy allyltin moiety
(11d) are provided in Table 6, in the experimental part. In the 2D
1H–119Sn HRMAS correlation spectrum (in C6D6), only the 119Sn
resonance at ꢀ29.8 ppm shows correlations with protons from
Scheme 8. Synthesis of supported a-substituted c-alkoxyallyltins 11a–d (R = Me, 11a; R = Et, 11b; R = i-Pr, 11c; R = t-Bu, 11d).
Table 5
Attempted preparations of supported
c-ethoxyallyltins via reaction of alkylcyanocuprates with 5bꢀE + Z, in the presence of BF3.OEt2.
Entry
R–M
CuCN
BF3.OEt2
solvent
Conversion (%)
1
2
3
4
MeLi.LiBr (6 eq.)
EtMgCl (6 eq.)
i-PrMgCl (6 eq.)
t-BuMgCl (6 eq.)
3 or 6 eq.
6 eq.
6 eq
3 or 6 eq
8 eq.
8 eq
THF or Et2O
Et2O
THF
0 (11a)
32 (11b)
47 (11c)
47 (11d)
3 eq
3 eq
Et2O

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G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
119Sn chemical shifts at 145 (broad signal), ꢀ7 and ꢀ9 ppm, as-
signed respectively to Sn–Cl, Sn–Et (transmetallation) and allyltin
11b. These samples were used for assessing the stereochemical
course of the reaction with benzaldehyde.
2.3. Assessment of the reactivity of the supported vinyltins and
allyltins
The results reported in Table 7 focus on the use of vinyltins in
Stille cross-coupling reactions and of allyltins in Lewis acid assisted
reactions on aldehydes.
The reactions performed with vinyl- or allyltin reagents grafted
to cross-linked polystyrene afford very similar results, both in
terms of yields and selectivity, when compared to reactions involv-
ing tributyltin analogues in homogeneous solution.
The experimental conditions used in solution for the vinyltrib-
utyltin derivatives can in general be extrapolated to supported
analogues, resulting in similar yields, but with the advantage of
minimizing pollution of final products by tin residues [9–11]. With
supported crotyltins we have already observed a slower 1,3–met-
allotropy when compared to crotyltributyltin [25], and in the case
of a-substituted c-ethoxyallyltins, their poor ability to give a 1,3-
metallotropy due to the stabilization occurring in the Z-isomer,
possibly because of coordination expansion of the tin atom by an
oxygen one, results in a regioselective reaction affording the
Fig. 5. Part of the 1H NOESY spectrum of 11d, recorded in C6D6 with a mixing time
of 50 ms, displaying cross-peaks between the vinylic proton resonances mutually
and between the vinylic proton resonances and their respective neighbours.
mono-protected
a-glycols. Comparison of the reaction using the
supported allyltin with its analogue in solution reveals that the
substituent (11c) shows very similar results (see Table 6 in exper-
imental part). The solid-state 119Sn MAS spectrum of the com-
pound with the ethyl substituent (11b) exhibits three isotropic
diastereoselectivity remains nearly unaffected. The anti-isomer
was obtained when the allyl unit contains a bulky
a-substituent,
while a syn preference remains the major pathway when this
Table 7
Reactivity of supported vinyltins and allyltins.
Entry
1
Substrate
Reagent
Conditions
Product
Yield or (conversion)a (%)
(100)[10]
Yield (%)b
65[16]
p-Br–C6H4–CHO
5
Pd(PPh3)4, toluene 110 °C, 40 h
OEt
OEt
OHC
2
p-Br–C6H4–OMe
5
Pd(PPh3)4, toluene 110 °C, 40 h
(78)[10]
67
OEt
OEt
MeO
Ph
3
4
Br–Ph
7
9
Pd(PPh3)4, toluene 110 °C, 40 h
49
85[17a]
OEt
OEt
Ph–CHO
InCl3, CH3CN
15 = (63) {Z/E: 72/28}
+ 16 = (9) {syn/anti: 99/1}
15 = 32 {Z/E: 60/40}
OH
+ 16 = 47 {syn/anti: 84/16}[25]
R1
Ph
R2
15, R1 = Me, R2 = H
+ 16, R1 = H, R2 = Me
5
6
7
Ph–CHO
Ph–CHO
Ph–CHO
11b
11c
11d
BF3.OEt2, CH2Cl2, 2 hꢀ78 °C
BF3.OEt2 , CH2Cl2, 2 hꢀ78 °C
BF3.OEt2, CH2Cl2, 2 hꢀ78 °C
(100) {syn/anti: 73/27}
(100) {syn/anti: 21/79}
(100) {syn/anti: 2/98}
82[33]{syn/anti: 72/28}
97[33]{syn/anti: 19/81}
92[33]{syn/anti: 3/97}
OH
Ph
OEt
OH
Ph
OEt
OH
Ph
OEt
a
Reactions carried out with supported vinyltins or allyltins, values in brackets are percentage conversions based on initial amounts of the supported organotin reagent.
Reactions carried out with the tributyltin analogues.
b

G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
1421
a
-substituent is an ethyl group. These results have been previously
4.3. Organotin synthesis procedures and characterization
4.3.1. Dibutylphenyltin hydride
rationalized by a competition between synclinal and antiperipla-
nar transition states [31].
Dibutylphenyltin hydride was obtained by reduction of the cor-
responding iodide according to the literature [8].
3. Conclusion
4.3.2. Poly[4-(di-n-butylhalogenostannyl)butyl]styrene compounds
3a-c
The results reported in this work are highly promising because
three original elements of information could be obtained:
(1) Among the synthetic methods used in solution, the hydro-
stannation of alkynes appears reasonably straightforward for the
synthesis of supported vinyltins. The same holds for the reaction
of organomagnesium or organozinc reagents with supported
organotin halides. Unfortunately, the use of much more complex
reagents like alkylcyanocuprates to modify functional vinyltin, still
requires major improvements for an efficient preparation of the
desired precursors. The possibility to prepare supported stannyla-
nions appears to be new and should allow the synthesis of prom-
ising functionalized targets;
The supported reagents were obtained according to literature
procedures by electrophilic cleavage of the supported phenyltin
analogue 2.
119Sn MAS NMR: data: 2: ꢀ43 ppm; 3a: 146 ppm; 3b: 130 ppm;
3c: 80 ppm
4.3.3. Poly[4-(di-n-butylhydridostannyl)butyl]styrene, 4
SnBu2H
(2) HRMAS NMR constitutes an invaluable tool to identify func-
tional groups linked to tin, for the determination of their structures
as well as for determining semi-quantitatively the relative
amounts of species or even isomers generated.
(3) Solid-state grafted vinyltins and allyltins display roughly the
same reactivity and diastereoselectivity patterns as their soluble
tributyltin analogues; since pollution by tin residues has been
shown to minimized to about 5–20 ppm, supported organotin re-
agents in general should afford interesting potentials in environ-
ment friendly organic synthesis, especially when the organotin
reagents are required in a late synthesis step.
A solution of LiAlH4 in THF (2.4 M, 1.69 mL, 4.06 mmol, 5 eq.)
was added dropwise under argon to a suspension of poly[4-(di-n-
butyliodostannyl)butyl]styrene 3c (0.7 g, 0.7 mmol) in dry THF
(8 mL) and the resulting mixture was stirred at 40 °C for 2.5 h in
the dark. The grafted material was successively washed, under ar-
gon, with THF (5 ꢁ 10 mL), absolute ethanol (2 ꢁ 10 mL) and dried
under vacuum (0.5 mbar) at 60 °C for 2 h. Compound 4 was ob-
tained as a white resin. d119Sn MAS NMR: ꢀ90 ppm.
4.3.4. Poly{4-[di-n-butyl-(3,3-diethoxyprop-1-en-2-yl)stannyl]butyl}
styrene, 5a
4. Experimental
4.1. General remarks
SnBu2
OEt
Starting materials were purchased from commercial suppliers
and used without further purification. Di-n-butyltin dichloride,
tri-n-butyltin chloride and tri-n-butyltin hydride were obtained
from Chemtura (Bergkamen). The polystyrene-divinylbenzene ma-
trix (Amberlite XE-305) was purchased from Interchim. THF was
distilled from sodium-benzophenone, toluene from sodium and
cyclohexane from CaH2 prior to use. TLC analyses were achieved
on silica-coated plates (Merck Kieselgel 60F254).
EtO
To a suspension of compound 3c (500 mg, 0.55 mmol) in dry THF
(5 mL) at ꢀ78 °C, a solution of 3,3-diethoxyprop-1-en-2-yllithium
in THF (10 mL, 1.1 mmol), obtained from 2-bromo-3,3-diethoxy-
prop-1-ene and t-BuLi, was added under argon. The resulting mix-
ture was then stirred at ꢀ78 °C for 3 h and allowed to warm up
slowly to room temperature in 2 h. Compound 5a was successively
washed with a mixture of THF/water (1:1 v/v, 20 mL), THF
(6 ꢁ 20 mL), absolute ethanol (4 ꢁ 20 mL) and dried under vacuum
(0.5 mbar) at 60 °C for 5 h.
4.2. NMR measurements
Solution NMR spectra were recorded on a Bruker Avance 300
spectrometer operating at 300.13 MHz for 1H, 75.47 MHz for 13C
and 111.92 MHz for 119Sn or on a Bruker ARX 400 spectrometer
operating at 400.13 MHz for 1H, 100.62 MHz for 13C and
149.21 MHz for 119Sn nuclei. Chemical shifts are given in ppm as
d values related to tetramethylsilane (1H, 13C) or tetramethyltin
4.3.5. Poly{4-[di-n-butyl-(3,3-diethoxyprop-1-en-1-yl)stannyl]
butyl}styrene 5b
OEt
(
119Sn) and scalar coupling constants are given in Hz.
HRMAS NMR spectra were recorded on a Bruker Avance 2 500
SnBu2
OEt
operating at 500.08, 125.75 and 186.48 MHz for 1H, 13C and 119Sn
nuclei, respectively, or on a 700 MHz Bruker Avance 2 spectrom-
eter operating at 700.13, 176.05 and 261.08 MHz, respectively,
each involving a dedicated Bruker 1H/13C/119Sn HRMAS probe
equipped with gradient coils. Sample rotors were filled with ca.
To a suspension of grafted derivative 4 (1.65 g, 1.65 mmol) in
dry THF (28 mL), 3,3-diethoxypropyne (0.356 mL, 2.48 mmol) and
a catalytic amount of AIBN were added under argon. The resulting
mixture was then stirred at 110 °C for 3 h. The insoluble material
was successively washed with a mixture of THF/water (1:1 v/v,
20 mL), THF (6 ꢁ 20 mL), absolute ethanol (4 ꢁ 20 mL) and dried
under vacuum (0.5 mbar) at 60 °C for 5 h. Compound 5 was ob-
tained as a white resin (1.9 g).
15 mg of resin beads, swollen in approximately 80 ll of CDCl3
or C6D6; magic angle spinning rate is ca 4 kHz. 1H and 13C chem-
ical shifts were determined from the residual solvent signal (7.26
and 77.0 ppm for CDCl3 and 7.15 and 128.0 ppm for C6D6 respec-
tively). 119Sn NMR measurements were referenced to
37.290665 MHz [34].
N =

1422
G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
4.3.6. Poly{4-[di-n-butyl-(3,3-diethoxyprop-1-yn-1-yl)stannyl]butyl}
styrene 6
reaction mixture is allowed to warm up until organocopper is
formed and then cooled down again to ꢀ78 °C. The reaction mix-
ture was stirred for 15 min and BF3ꢂOEt2 (4.0 or 8.0 equiv.) was
added. After stirring for 20 min, the reaction mixture was trans-
ferred through a canula onto 5b(E+Z) (1 equiv., 440 mg, 0.5 mmol)
and the resulting mixture was stirred at ꢀ50 °C for 17 h. The reac-
tion mixture was hydrolyzed with a saturated solution of NaHCO3
and, after filtration, the insoluble material was successively
washed with a mixture of THF/aqueous NH4Cl (1:1 v/v, 10 mL),
THF (6 ꢁ 10 mL), absolute ethanol (4 ꢁ 10 mL) and dried under
vacuum (0.5 mbar) at 60 °C for 5 h.
OEt
SnBu2
OEt
To a suspension of grafted derivative 3c (500 mg, 0.55 mmol) in
dry THF (5 mL) at ꢀ78 °C, a solution of 3,3-diethoxyprop-1-yn-1-
yllithium in THF (10 mL, 1.1 mmol), obtained from 3,3-diet-
hoxypropyne and n-BuLi, was added under argon. The resulting
mixture was then stirred at ꢀ78 °C for 3 h and allowed to warm
up slowly to room temperature in 2 h. Compound 6 was succes-
sively washed with a mixture of THF/water (1:1 v/v, 20 mL), THF
(6 ꢁ 20 mL), absolute ethanol (4 ꢁ 20 mL) and dried under vacuum
(0.5 mbar) at 60 °C for 5 h.
4.3.9.1. Poly{4-[di-n-butyl(1-ethoxy-penten-3-yl)stannyl]butyl}sty-
rene 11b.
OEt
SnBu2
1H HRMAS NMR (CDCl3): 0.92 (CH2,
(CH3), 1.36 (CH2, Sn), 1.61 (CH2, b Sn), 3.60 (1H, CH2), 3.77 (1H,
CH2), 5.25 (1H, CH) ; 13C HRMAS NMR (CDCl3): 11.2 (CH2,
Sn),
13.8 (CH2, d Sn), 15.2 (CH3), 26.7 (CH2, Sn), 28.9 (CH2, b Sn),
60.7 (CH2O), 89.2 (C,
Sn), 91.4 (CH), 104.9 (C, b Sn); 119Sn HRMAS
a Sn), 1.05 (CH2, d Sn), 1.22
δ
119Sn MAS NMR: −29 ppm.
c
a
c
a
4.3.9.2.
Poly{4-[di-n-butyl(1-ethoxy-4-methyl-penten-3-yl)stan-
NMR (CDCl3): ꢀ64.5 ppm.
nyl]butyl}styrene 11c andPoly{4-[di-n-butyl(1-ethoxy-4,4-dimethyl-
penten-3-yl)stannyl]butyl}styrene 11d.
4.3.7. Poly{4-[di-n-butyl-(4,4-diethoxybut-1-en-1-yl)stannyl]butyl}
styrene 7
OEt
11c
OEt
SnBu2
SnBu2
OEt
11d
SnBu2
OEt
4.4. Stille cross-coupling involving supported vinyltins and alkynyltins
4.3.8. Poly[4-(di-n-butyl-crotyl-stannyl)butyl]styrenes 9 (+ 10)
4.3.8.1. Preparation using Barbier conditions. To a suspension of 3c
(500 mg, 0.55 mmol) and zinc powder (30 mesh, 2.75 mmol) in
dry THF (10 mL), crotylchloride (E/Z : 85/15 ; 2.75 mmol) was
added and the resulting mixture was stirred at 45 °C for 18 h.
The insoluble material was successively washed, under argon,
with THF/water (1:1 v/v, 10 mL), THF (6 ꢁ 10 mL), absolute eth-
anol (4 ꢁ 10 mL) and dried under vacuum (0.5 mbar) at 60 °C for
2 h.
4.4.1. General procedure for the Stille cross-coupling reaction
In an oven-dried Schlenk flask compound 5, 6 or 7 (1.1 equiv.),
the halide aryl (1.0 equiv.), catalyst (0.05 equiv.) and dry solvent, as
mentioned in the Table 7, were successively added under argon.
The reaction mixture was then heated up to reflux temperature.
The insoluble material was washed with THF (6 ꢁ 10 mL) and the
filtrate was concentrated under vacuum. The resulting crude resi-
due was analyzed by GC, and was subsequently purified by column
chromatography using silica gel. (Petroleum ether/AcOEt: 9/1).
Otherwise, the resulting insoluble material was washed with abso-
lute ethanol (4 ꢁ 10 mL) and dried under vacuum (0.5 mbar) at
60 °C for 5 h.
4.3.8.2. Preparation using a supported stannylanion. To a suspension
of grafted organotin hydride 4 (500 mg, 0.5 mmol) in dry THF
(10 mL) at 0 °C, was added, under argon, a solution of lithium diiso-
propylamide (1 M in THF, 0.5 mmol). The resulting mixture was
then stirred at 0 °C for 30 min; subsequently, crotylchloride was
4.4.2. 4-[3,3-diethoxyprop-1-en-1-yl]benzaldehyde, 12.
added (E/Z: 85/15, 50 lL, 0.5 mmol). The resulting mixture was
then stirred at 0 °C for 30 min, thereafter 18 h at room tempera-
ture. The insoluble material was successively washed with a mix-
ture of THF/water (1:1 v/v, 20 mL), THF (6 ꢁ 20 mL), absolute
ethanol (4 ꢁ 20 mL) and dried under vacuum (0.5 mbar) at 60 °C
for 5 h.
OHC
CH(OEt)2
HRMS (EI) Calc. for C14H18O3: 234.1256. Found: 234.1256.
isomer E: 1H NMR (400 MHz; CDCl3): 1.26 (t, 3H, 3J = 7), 3.58 (dq,
2H, 2J = 9.4, 3J = 7), 3.72 (dq, 2H, 2J = 9.4, 3J = 7), 5.10 (dd, 1H, 3J = 4.9,
3J = 1.2), 6.36 (dd, 1H, 3J = 16.1, 3J = 4.9), 6.78 (dd, 1H, 3J = 16.1,
4.3.9. Synthesis of supported
a-substituted
c
-alkoxyallyltins 11b–d
OEt
4J = 1.2), 7.55 (d, 2H, 3J = 8.0), 7.84 (d, 2H, 3J = 8.0), 9.99 (s, 1H); 13
C
R
NMR (100.62 MHz, CDCl3): 15.3 (2C), 61.3 (2C), 100.9, 129.6 (2CAr),
130.1 (2CAr), 130.5, 131.7, 135.8 (CIVAr), 142.3 (CIVAr), 191.6. MS
(EI): m/z = 234 (13), 206 (3), 205 (4), 189 (100), 177 (3), 163 (26),
161 (47), 160 (13), 147 (8), 135 (14), 133 (62), 132 (30), 131 (39),
115 (42), 105 (25), 103 (40), 91 (11), 79 (9), 77 (30), 75 (7), 55 (25).
isomer Z: 1H NMR (400 MHz; CDCl3): 1.22 (t, 3H, 3J = 7.1), 3.56
(dq, 2H, 2J = 9.5, 3J = 7.1), 3.67 (dq, 2H, 2J = 9.5, 3J = 7.1), 5.19 (dd,
SnBu2
To a suspension of copper(I) cyanide (3.0 or 6.0 equiv.) in dry
THF (10 mL), a solution of organometallic reagent (RM) in diethyl
ether (3.0 or 6.0 equiv.) was added, at ꢀ78 °C, under argon. The

G. Kerric et al. / Journal of Organometallic Chemistry 695 (2010) 1414–1424
1423
1H, 3J = 7.3, 4J = 1.1), 5.93 (dd, 1H, 3J = 12.0, 3J = 7.3), 6.68 (bd, 1H,
3J = 12.0), 7.55 (d, 2H, 3J = 8.0), 7.86 (d, 2H, 3J = 8.0), 10.0 (s, 1H);
13C (100.62 MHz, CDCl3): 15.2 (2C, CH3), 60.6 (2C, CH2O), 97.6,
129.6 (2C, CHAr), 129.7 (2C, CHAr), 131.5 (Ar–CH@), 132.1, 135.3 (CI-
VAr), 142.4 (CIVAr), 191.7. MS (EI): m/z = 234 (11), 206 (5), 205 (10),
189 (100), 177 (4), 163 (26), 161 (52), 160 (15), 147 (8), 135 (12),
133 (68), 132 (32), 131 (47), 115 (49), 105 (27), 103 (53), 91 (12),
79 (10), 77 (36), 75 (14), 55 (31), 47 (10).
quenched with HCl (0.1 M, 10 mL). The crude insoluble material
was filtered and washed with diethyl ether (6 ꢁ 30 mL) and then
with THF (6 ꢁ 30 mL). The filtrate was extracted with diethyl ether
and washed with brine (50 mL), dried over MgSO4 and concen-
trated in vacuum.
Compounds 15-E, 15-Z, 16-syn and 16-anti have been previ-
ously characterized [25,35].
4.5.2. Allylation of benzaldehyde by supported c-ethoxyallyltins
4.4.3. 1-[3,3-diethoxyprop-1-en-1-yl]-4-methoxybenzene, 13
To a suspension of grafted derivative 11 (150 mg) in dry CH2Cl2
(2 mL), benzaldehyde (0.014 mL, 0.14 mmol) and, dropwise at
ꢀ78 °C, a solution of BF3ꢂOEt2 (0.076 mL, 0.6 mmol) were added
under argon. The reaction mixture was stirred at ꢀ78 °C for 2 h
and was then quenched with a mixture of THF/aqueous NaHCO3
(1:1 v/v). The insoluble material was filtered and washed with
THF (6 ꢁ 10 mL). The filtrate was extracted with diethyl ether
(3 ꢁ 20 mL), washed with brine (50 mL), dried over MgSO4 and
concentrated under vacuum. The resulting crude residue was ana-
lyzed by GC. Otherwise, the resulting insoluble material was
washed with absolute ethanol (4 ꢁ 10 mL) and dried under vac-
uum (0.5 mbar) at 60 °C for 5 h.
MeO
CH(OEt)2
HRMS (EI) Calc. for C14H20O3: 236.1412. Found: 236.1412.
Isomer E: 1H NMR (400 MHz; CDCl3): 1.24 (t, 6H, 3J = 7.1, CH3),
3.64 (dq, 2H, 2J = 9.5, 3J = 7.1), 3.64 (dq, 2H, 2J = 9.5, 3J = 7.1), 3.83 (s,
3H), 5.06 (d, 1H, 3J = 5.3, 4J = 1.1), 6.09 (d, 1H, 3J = 16.1, 3J = 5.3),
6.67 (bd, 1H, 3J = 16.1), 6.87 (d, 2H, 3J = 8.4), 7.36 (d, 2H, 3J = 8.4).
13C NMR (100.62 MHz, CDCl3): 15.3 (2C), 55.3, 61.0 (2C), 101.8,
113.9 (2CAr), 124.5, 128.2 (2CAr), 132.4, 154.1 (CIVAr), 159.6 (CIVAr).
MS EI: m/z = 236 (16), 207 (29), 191 (100), 165 (24), 163 (36), 161
(12), 145 (17), 135 (24), 131 (12), 121 (13), 103 (9), 91 (12), 55
(15).
The characterization of compounds 17–19 has been previously
reported including the assignment of the syn or anti configuration
of the homoallylic alcohols [33].
Acknowledgments
Isomer Z: 1H NMR (400 MHz; CDCl3): 1.22 (t, 6H, 3J = 7.1), 3.45
(dq, 2H, 2J = 9.6, 3J = 7.1), 3.53 (dq, 2H, 2J = 9.6, 3J = 7.1), 3.83 (s, 3H),
4.83 (dd, 1H, 3J = 5.1, 4J = 1.2), 6.23 (dd, 3J = 13.4, 4J = 1.2), 6.54 (dd,
We are grateful to Egide programs (PHC Tournesol FL
N°13963YC), to CNRS (Réseau de Recherche 2: « Aller vers une Chi-
mie Eco-compatible ») and to ANR (Grant No JC07_209849) for
financial support. We wish also to acknowledge MENRT for a doc-
toral fellowship (G.K.) and Chemtura (Bergkamen) for the gift of
dibutyltin dichloride, tributyltin chloride and tributyltin hydride.
M.B. and R.W. are indebted to the Flemish Fund for Scientific Re-
search (FWO Flanders, Belgium; Grant No.0469.06) and to the Re-
search Council of the VUB (Grant No GOA31).
1H, 3J = 13.4, 3J = 5.1), 6.88 (d, 2H, 3J = 8.4), 7.35 (d, 2H, 3J = 8.4). 13
C
NMR (100.62 MHz, CDCl3): 15.3 (2C), 55.3, 60.9 (2C), 102.3, 113.9
(2CAr), 128.2 (2 CAr), 134.2, 144.7, 154.1 (CIVAr), 159.6 (CIVAr). MS
(EI): m/z = 236 (16), 207 (33), 191 (100), 165 (28), 163 (39), 161
(14), 145 (21), 135 (27), 131 (12), 103 (10), 91 (15), 55 (20).
4.4.4. [(1E)-4,4-diethoxybut-1-en-1-yl]benzene, 14
References
CH(OEt)2
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(b) J.A. Marshall, Chem. Rev. 96 (1996) 31–48;
Isomer E: 1H NMR (400 MHz; CDCl3): 1.24 (t, 6H, 3J = 7), 2.56
(ddd, 2H, 4J = 1.4, 3J = 5.7, 3J = 7.1); 3.56 (dq, 2H, 3J = 7.0, 2J = 9.5),
3.70 (dq, 2H, 3J = 7.0, 2J = 9.5), 4.59 (t, 1H, 3J = 5.7), 6.21 (dt, 1H,
3J = 15.9, 3J = 7.1), 6.50 (dt, 1H, 3J = 15.9, 3J = 1.4), 7.21-7.37 (m,
5H). 13C NMR (100.62 MHz, CDCl3): 15.3 (2C), 37.8 , 61.4 (2C),
102.6, 125.3, 126.1 (2CAr), 127.1 (CAr), 128.5 (2C, Ar), 132.4, 137.6
(CIVAr). MS CI(NH3): m/z = 238 (2), 192 (4), 175 (57), 163 (32),
146 (100), 103 (29).
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trends in the synthesis of solid-supported organotin reagents, in: A.G. Davies,
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(1990) 448–452;
(b) W.P. Neumann, M. Peterseim, React. Polym. 20 (1993) 189–205;
(c) G. Dumartin, J. Kharboutli, B. Delmond, Y. Frangin, M. Pereyre, Eur. J. Org.
Chem. (1999) 781–783;
(d) G. Ruel, K.T. Ngo, G. Dumartin, B. Delmond, M. Pereyre, J. Organomet.
Chem. 444 (1993) C18–C20;
Isomer Z: 1H NMR (400 MHz; CDCl3): 1.21 (t, 6H, 3J = 7.0), 2.69
(ddd, 2H, 4J = 1.9, 3J = 5.9, 3J = 7.3), 3.52 (dq, 2H, 3J = 7.0, 2J = 9.5),
3.65 (dq, 2H, 3J = 7.0, 2J = 9.5), 4.6 (t, 1H, 3J = 5.9), 5.73 (dt, 1H,
3J = 12.0, 3J = 7.3), 6.55 (dt, 1H, 3J = 12.0, 4J = 1.9), 7.21–7.37 (m,
5H). 13C NMR (100.62 MHz, CDCl3): 15.3 (2C), 33.3 (CH–CH2),
61.2 (2C), 102.4, 126.7, 128.1 (2CAr), 128.2 (1CAr), 128.8 (2CAr),
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