Preparation of allyltin reagents grafted on solid support: Clean and easily recyclable reagents for allylation of aldehydes

Article abstract of DOI:10.1002/chem.200501595

The preparation of polymer-supported allyltin reagents was shown to be possible for both unfunctionalized and functionalized allyl units. These reagents were treated with aldehydes in the presence of cerium(III) or indium(III) salts to afford high yields

Full text of DOI:10.1002/chem.200501595

DOI: 10.1002/chem.200501595
Preparation of Allyltin Reagents Graftedon SolidSupport: Clean andEasily
Recyclable Reagents for Allylation of Aldehydes
[
a]
[a]
[a]
Jean-Mathieu ChrØtien, FranÅoise Zammattio,* Delphine Gauthier,
[
a]
[b]
[a]
Erwan Le Grognec, Michal Paris, andJean-Paul Quintard*
Abstract: The preparation of polymer-supported allyltin reagents was shown to be
possible for both unfunctionalized and functionalized allyl units. These reagents
were treated with aldehydes in the presence of cerium
A
H
R
U
G
A
H
R
U
G
Keywords: aldehydes · allylation ·
afford high yields of homoallylic alcohols, practically uncontaminated with organo-
tin residues (less than 5 ppm). Some mechanism aspects are briefly discussed and
the potential for regeneration and reuse of these supported reagents is pointed
out.
polymer-supported
recycling · tin
reagents
·
Introduction
the well established solution-phase reactions involving orga-
nometallic compounds or transition-metal complexes to
solid supports. Accordingly, the use of supported reagents
The development of new synthetic methods that are envi-
ronmentally benign is of great interest today. One important
strategy for this purpose involves the use of supported re-
[4]
has recently been applied to free radical chemistry, cross-
[
5]
[6]
[7]
coupling reactions, olefin metathesis, oxidation, halo-
[
1]
[8]
[9]
agents or catalysts. The immobilization of transition-metal
catalysts and certain organometallic compounds, in order to
control the pollution from these species at trace levels (a
few ppm), has attracted a lot of attention, especially when
compounds of biological or pharmaceutical interest are con-
cerned. Moreover, immobilized reagents on polymer sup-
ports are particularly well suited for parallel and high-
throughput syntheses, due to their well known properties of
dispersal and removal from reaction mixtures. Further-
more, the potential to recycle these polymer-bound reagents
and catalysts also constitutes a highly desirable goal. In
this context, considerable efforts have been made to transfer
genation, and reduction reactions. In comparison, poly-
mer-supported allylmetal reagents remain relatively unex-
plored, and in particular the preparation of polymer-sup-
[10]
ported allylstannanes and their use in the allylation of al-
dehydes have not yet received much attention even though
this polymer-supported chemistry should display major ad-
vantages in terms of ease of use, ease of removal of the tin
residues from the desired products, and potential for recy-
cling the supported tin reagents.
[2]
To the best of our knowledge, only a few examples of the
use of immobilized allyltin reagents in allylation of alde-
hydes have been reported. Dumartin et al. have developed
the polymer-supported dibutylallyltin reagent 1a, synthe-
sized by treatment of an allyl Grignard reagent with an io-
[3]
[
a] Dr. J.-M. ChrØtien, Dr. F. Zammattio, D. Gauthier,
Dr. E. Le Grognec, Prof. Dr. J.-P. Quintard
UniversitØ de Nantes, CNRS
Laboratoire de Synth›se Organique, UMR 6513
FacultØ des Sciences et des Techniques
[11]
dotriorganostannylated resin,
whilst Cossy and Marshall
have described the synthesis of the polymer-supported (a-al-
koxycrotyl)tributyltin 2 by coupling a commercially availa-
ble carboxylic polystyrene resin with an (a-hydroxycrotyl)-
2
rue de la Houssini›re, BP 92208, 44322 Nantes cedex 3 (France)
[12]
Fax : (+33)251-125-402
tributylstannane.
In both instances the authors pointed
E-mail: francoise.zammattio@univ-nantes.fr
jean-paul.quintard@univ-nantes.fr
out that these new allylstannanes grafted onto polystyrene
resin could be used for the allylation of aldehydes either
with the aid of BF ·OEt or through transmetalation with
[
b] Dr. M. Paris
3
12]
2
UniversitØ de Nantes, CNRS
Institut des MatØriaux Jean Rouxel, UMR 6502
[
indium tribromide.
More recently, Gastaldi et al. have
prepared soluble polyaromatic hydrocarbons (PAHs)bear-
2
rue de la Houssini›re, BP 32229, 44322 Nantes cedex 3 (France)
ing an allyltin unit 3 and have shown their usefulness in
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author.
[13]
both radical and ionic allylations.
An allylstannane re-
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Chem. Eur. J. 2006, 12, 6816 – 6828

FULL PAPER
agent 4 grafted onto a soluble non-cross-linked polystyrene
support was also obtained by Enholm and shown to be effi-
cient in the free radical allylation reaction of organic hal-
Results andDiscussion
Preparation of the polymer-supported di - n-butylallyltin re-
agents of type 1a–d: The usual synthetic routes to allyltrior-
ganotins in solution include treatment of triorganotin hal-
[
10]
ides (Scheme 1).
[15]
ides or triorganotin oxides with allylic Grignard reagents,
[
16]
[17]
allyllithiums, or allylzinc reagents. Hydrostannation of
either 1,2- or 1,3-dienes under free radical conditions or
[18,19]
with palladium catalysis,
as well as stannylcupration of
[20]
allenes, have also been employed to obtain allyltins, but
difficulties were encountered in controlling the regio- and/or
the stereochemistry of the reactions. Tin hydrides have also
been used to prepare allyltins from allylsulfones and related
[
21]
compounds. While they are easy to carry out in terms of
workup, the above preparations usually suffer from a lack of
regio- and stereospecificity when g-substituted allyl units are
involved (mixture of isomers are obtained), although syn-
thetic methods involving deprotonation reactions by organo-
lithium reagents based either on crotyl carbamates in the
Scheme 1.
In spite of the considerable improvements brought by
these supported reagents, both for easy recovery of the
products and for limitation of the tin contamination, further
improvements can be reasonably suggested. In the case of
the immobilized reagent 1a, attachment of the scaffold was
achieved by use of allylmagnesium reagents, which are in-
compatible with the presence of functionalities such as
esters or nitriles, whilst in the case of the polymer-bound re-
agent 2, the functional crotyltin unit is grafted to the solid
support through an ether linkage instead of a tin–carbon
linkage, a situation that may complicate the recycling of the
reagents, due to the poor stabilities of a-hydroxyorganostan-
nanes, and that might also make complete control of tin pol-
lution more difficult.
Finally, with soluble polymers, the separation and the iso-
lation of the desired reaction products is usually less easy,
because it is necessary to induce the precipitation of the
macromolecular support with an appropriate solvent.
Thus, in view of the above remarks, and in conjunction with
our recent involvement in the synthesis of polymer-support-
ed organometallic reagents, we investigated a new route
to insoluble polymer-supported allylstannanes allowing the
presence of functional groups on the allylic moiety. Here we
describe a general and efficient route to immobilized allyltin
reagents of type 1 by treatment of suitably substituted allyl-
zinc reagents 6 with the resins 5 used as triorganostannyl
halides (Scheme 2). We also evaluated the potential of these
C-linked reagents 1a–d in the allylation of a series of alde-
hydes, focusing both on the tin contamination in the isolated
homoallylic alcohols and on the potential for recycling these
new immobilized reagents.
[22]
[23]
presence of (À)-sparteine or on chiral allylic substrates
have been reported to overcome these limitations satisfacto-
rily in some cases. In practice, the problems encountered
with the selectivity of the reactions can be more easily cir-
cumvented by the use of stannylanions, which can be used
[24]
to achieve S 2 reactions with allyl tosylates or chlorides
N
or 1,4-additions on a,b-enals. (E) - or (Z )-g-oxygenated allyl-
tins can also be selectively obtained through 1,4-additions of
[25]
organocuprates to b-tributylstannylacroleine, and in these
series, when enantioenriched alkoxyallyltins are desired, the
[26]
available highly enantioenriched a-oxygenated allyltins
can be stereospecifically isomerized into the g-oxygenated
[27]
isomers.
Obviously, the use of stannyl anions should be of high in-
terest for selectivity, but in a first step we needed to exam-
ine the use of more conventional reagents to establish the
effective availability of supported allyltins and to evaluate
their potential as recyclable allylation reagents. Initially
then, to test compatibility with functional groups on the re-
agent, we decided to attempt direct coupling of organozinc
reagents with triorganotin halides, a route that has not been
[10,13]
[14]
[5d]
extensively explored.
When carried out in liquid phase, the reactions between
[28]
allylzinc reagents 6a–d
and tributyltin chloride afforded
the corresponding allyltins 7a–d in fairly good isolated
yields [Eq. (1)].
These results suggest that it
should be possible to synthesize
a series of triorganoallyltin re-
agents grafted onto solid sup-
port by adding organozinc re-
Scheme 2. Synthetic strategy.
Chem. Eur. J. 2006, 12, 6816 – 6828
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6817

F. Zammattio, J.-P. Quintard et al.
agents 6 to a resin containing triorganotin halide units. For
dSn = +80.5 ppm and around dSn = À15 ppm was indicative
of incomplete conversion (Table 1, entries 2–4).
this purpose, we chose the already known polymer-support-
[9a–e,14]
ed triorganotin iodide 5a,
which seemed to be among
In an effort to improve these results, we turned our atten-
tion to Tagliaviniꢁs procedure, which involves the one-pot
synthesis of triorgano- and diorganoallyltins through a zinc-
promoted coupling reaction between allyl bromide and
R SnX (X = Cl, I, OH, etc.), Bu SnCl , or (Bu SnCl) O in
the more suitable ones for our solid-phase applications be-
cause of its ease of formation and good loading (1.1 to
À1
1
.3 mmolg ). A series of immobilized triorganoallyltin re-
agents 1a–d was thus prepared from polymer 5a and appro-
priate allylzinc reagents 6a–d [Eq. (2)]. The results are sum-
marized in Table 1.
3
2
2
2
2
[17,31]
the presence of air and water.
We have confirmed its ef-
ficiency for the synthesis of 7a and 7b (81 and 88% yields,
respectively)and have shown
its possible extension to func-
tionalized allyl halides for the
synthesis of 7c and 7d (87 and
9
1% yields)by treatment of
suitable allyl bromides with
Bu SnCl and zinc powder in a
3
Table 1. Preparation of polymer-supported allyltin reagents 1a–d with al-
lylzincs.
THF/H O
(NH Cl-saturated)
4
2
mixture. The allylation of resin 5a over 16 h under similar
experimental conditions was also investigated, but
Sn MAS-NMR analysis of the collected resin particles
successively washed with THF and absolute ethanol and
[
a]
Entry
Allylzinc 6
Resin 1
Conversion [%]
1
2
3
4
6a: R = H
6b: R = CH
6c: R = COOEt
6d: R = CN
1a: R = H
1b: R = CH
3
1c: R = COOEt
1d: R = CN
94
88
75
53
119
3
(
dried under vacuum)revealed a failure of this strategy to
provide polymer-supported allyltins 1a–d. The starting resin
5a was recovered except in the case of 1c (R = COOEt),
in which a low conversion (30%)was observed. This result
may be explained by the large amount of water in THF,
1
19
[
a] Conversion determined by Sn MAS-NMR with use of an appropri-
ate repetition time for quantitative analysis.
[32]
In a typical procedure, a solution of allylzinc 6a–d in THF
was added under argon to a mixture of solid-supported tin
reagent 5a in THF and the reaction mixture was stirred for
which is incompatible with the polystyrene resin: the pore
structure cannot fill with the co-solvent, preventing access
of the organozinc reagents to the polymer network.
1
6 h at 458C before workup and filtration. The expected
Accordingly, the reaction was subsequently achieved at
458C in anhydrous THF. These experimental conditions,
much more favorable for a good swelling of resin 5a, al-
lowed the desired reaction with a high level of conversion,
polymer-supported tin reagents 1a–d were then successively
washed with THF and absolute ethanol and were then dried
under vacuum. The formation of the polymer-supported tri-
organoallyltin reagents 1a–d was established through their
IR spectra, each of which exhibits a well defined band
1
19
as determined by solid-state Sn NMR (Scheme 3). As can
À1
around 1620 cm , indicative of the C=C double bond of the
allylic moiety. The presence of additional functionality on
the allylic unit was also characterized by specific IR absorp-
À1
tions (band at 1720 cm in the case of resin 1c and weak
À1
band at 2200 cm in the case of 1d). Chemical information
Scheme 3.
on the tin environment was also well established through
119
solid-state Sn MAS-NMR analysis, allowing us to ascer-
[
29,9c–d]
tain the levels of conversion of resin 5a to resins 1a–d.
be seen in Table 2 (entries 1–4), this method appears to be
highly efficient for the preparation of the series of polymer-
Indeed, comparison of the relative intensities of the signal
due to the polymer-supported
triorganotin iodide 5a with
those due to the supported al-
lyltins was indicative of the con-
Table 2. One-pot synthesis of polymer-supported allyltins 1a–d.
Conversion [%] d 119Sn MAS-NMR Tin loading [mmolg
[a]
[b]
À1
Entry Allyl halide 8
Resin 1
]
1
2
3
4
8a: R = H
8b: R = CH3
8c: R = COOEt 1c: R = COOEt 99
8d: R = CN 1d: R = CN 94
1a: R = H
1b: R = CH3
100
95
À18.5
À17.5
À12.1
À9.5
1.41
1.11
1.23
1.19
version rate of SnÀI (d
=
Sn
+
=
80.5 ppm)into Sn ÀAllyl (d
Sn
À9.5 to À18.5 ppm)(refer-
1
19
ence:
À121.1 ppm).
Ph Sn,
d
=
[a] Conversion determined by Sn MAS-NMR spectroscopy. [b] Tin loading determined by elemental analy-
sis.
4
Sn
[30]
The complete
disappearance of the signal due
to 5a in the case of polymer 1a was regarded as evidence of
a nearly quantitative conversion (Table 1, entry 1). For poly-
mers 1b–d, however, the presence of two typical signals at
supported allyltins 1a–d. Moreover, our procedure does not
require prior preparation of the allylzinc reagents 6a–d, so
the polymer-supported allyltins 1a–d are directly obtained
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Allyltin Reagents on Solid Support
FULL PAPER
in a one-pot process with nearly quantitative loading as de-
termined by solid state Sn NMR (1.1–1.4 mmolg ).
allylation reactions without the use of anhydrous solvents,
1
19
À1
inert atmosphere, and low temperature. CeCl ·7H O
3
2
seemed to be an attractive candidate for use as a Lewis acid
in our solid-phase application in this context, due to its
water tolerance and ready availability at low cost. Among
Allylation reactions between aldehydes and polymer-sup-
portedallyltriorganotins 1a –d: The grafting rates and the
natures of the substituents around tin being well established
in supported allyltins 1a–d, we therefore checked their effi-
ciency in the allylation reactions of various aldehydes. Ini-
tially we carried out the allylation reaction with benzalde-
hyde in the presence of resins 1a–c and BF ·OEt as Lewis
[33]
the numerous methodologies that employ cerium(iii)de-
A
C
H
T
R
E
U
N
G
rivatives for transferring nucleophile moieties to electrophil-
ic centers, the allylation of aldehydes promoted by the
CeCl ·7H O/NaI (10%)system as a Lewis acid appeared to
3
2
[34]
be a possible route, so we examined the efficiency of this
system in acetonitrile for the allylation of a series of alde-
3
2
acid promoter under anhydrous conditions [Eq. (3)]. For
this purpose, resin 1a–c, benzal-
dehyde, and CH Cl
were
2
2
placed in a flask under argon
and BF ·OEt2 (3 equiv)was
3
added dropwise at À788C. The
results are summarized in
Table 3.
hydes
Eq. (4)].
The reactions were conduct-
ed by heating a mixture of resin
a–d in acetonitrile containing
the aldehyde and the
CeCl ·7H O/NaI (10%)combi-
with
resins
1a–d
[
1
3
2
nation (in suitable tubes for
parallel synthesis equipment,
with use of ellipsoidal stirring)at 60 8C for 24 to 48 h
Table 3. Allylation of benzaldehyde in the presence of resins 1a–c and
(
1
Table 4). Good yields were obtained with the resins 1a and
b whatever the nature of the aldehydes, while functional-
with BF
3
·OEt
2
as a Lewis acid promoter.
[
a]
[b]
Entry Resin
Homoallylic alcohols Conversion
Yields
[%]
ized allyltin resins 1c and 1d appear to be nearly unreactive
under these experimental conditions, a result that might be
due either to insufficient Lewis acid character of the hydrat-
ed cerium salt or to competitive chelation on the b-function-
al group.
1
9
[%]
1
2
3
1a
1b
1c
9a
9b
9c
ꢀ100
92
ꢀ100
61
67
83
[
a] Conversion determined by GC. [b] Yield of isolated pure compound
after column chromatography on silica gel.
To circumvent the lack of reactivity of 1c and 1d in allyla-
tion promoted by cerium
other Lewis acids to promote this reaction and found that
the use of indium(iii)bromide or chloride [Eq. (5 )] was also
A
H
R
U
G
After stirring for 2 h at À788C and subsequent quenching
ACHTREUNG
with a mixture of THF/H O
2
(
1:1 v/v), the conversion rates
of the crude homoallylic alco-
hols were comparable to
9
those obtained with soluble al-
lyltins. It is worth noting that
the reaction is unaffected by
the presence of the ester func-
tion in the b-position (Table 3,
entry 3).
While this first approach had proved acceptable, improve-
ments were sought to make the methodology amenable to
automated parallel synthesis. The strictly anhydrous condi-
tions and the low temperatures required with the use of
BF ·OEt to promote the allylation of aldehydes are unsuita-
efficient, as attested by the results shown in Table 5 and con-
sistently with previous reports concerning reactions achieved
[35]
in liquid phase. Good yields were uniformly obtained with
InBr as a promoter in this series, and InCl was shown to
3
3
have nearly the same efficiency when tested on two exam-
ples.
3
2
ble for easy handling and manipulation, so we devoted our
efforts to finding experimental conditions that would allow
Chem. Eur. J. 2006, 12, 6816 – 6828
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6819

F. Zammattio, J.-P. Quintard et al.
3 2
Table 4. Allylation of a series of aldehydes with resins 1a and 1b in the presence of CeCl ·7H O/NaI (10%)as a promoter.
[
a]
[b]
[c]
Entry
Aldehyde
Product
Time [h]
Yield [%]
Sn [ppm]
Ce [ppm]
1
9a: R = H
b: R = Me
30
36
95
90
3.8Æ0.2
<0.10
9
2
3
4
5
10a: R = H
0b: R = Me
24
24
99
91
1.6Æ0.1
2.8Æ0.2
<0.10
1
0.28Æ0.02
11a: R = H
1b: R = Me
30
30
97
92
2.5Æ0.2
3.3Æ0.2
1.1Æ0.1
<0.10
1
12a: R = H
2b: R = Me
48
48
82
78
<0.10
1
13a: R = H
3b: R = Me
48
48
83
89
0.11Æ0.01
1
6
7
14a
15a
30
48
85
93
6.0Æ0.3
0.16Æ0.01
8
9
16a
17a
60
48
74
77
10
11
12
18a
19a
20a
48
62
60
86
88
85
1.0Æ0.1
<0.10
1
3
4
21a
22a
96
48
68
87
1.9Æ0.3
1.7Æ0.1
<0.10
<0.10
1
1
5
6
23a
24a
48
48
89
82
1
[
a] Yield of isolated product after column chromatography. [b] Quantification of tin residues in the homoallylic alcohols determined by ICP-MS (average
of three runs). [c] Quantification of cerium residues in the homoallylic alcohols determined by ICP-MS (average of three runs).
6820
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Allyltin Reagents on Solid Support
FULL PAPER
Table 5. Allylation of aldehydes with resins 1a, 1c, and 1d with InBr
3
or InCl
3
as a promoter.
of the involved mechanism.
Yields [%] Thus, the crotylstannation of
benzaldehyde under the experi-
[
a]
Entry
Resin 1
Aldehyde
Product
mental conditions used for the
reactions involving supported
1
1a
9a
94
allyltriorganotins afforded
mixture of branched and linear
homoallylic alcohols 26 and 27
a
9
9
9
7
2
3
1a
1a
10a
[
b]
c]
[
Eq. (6)].
[
11a
95
While 26 had been obtained
as
a single product with a
strong preference for the syn
isomer (syn/anti 82:18)from
the reaction carried out in the
presence of boron trifluoride
4
5
6
1a
1c
1c
12a
9c
84
91
(
as would be expected from the
[36]
opened transition state),
the
reactions performed in the
9
9
6
3
10c
[
b]
presence of CeCl ·7H O or in
3
2
the presence of InCl or InBr3
3
afforded mixtures of 26 and 27.
The major isomer, however,
was syn-26 (syn/anti 70:30 to
7
8
9
1c
1c
1d
11c
12c
11d
92
72
73
8
4:16), which is consistent with
an opened transition state, be-
cause the six-membered transi-
tion state should mainly give
the anti isomer. Furthermore,
with cerium or indium salts, the
linear adduct 27 was obtained
mainly as the Z isomer, a trend
that might be explained by a
[
a] Yield of isolated product after column chromatography with use of InBr
3
as a promoter unless mentioned
otherwise. [b] Reaction carried out with InCl
by ICP-MS and found to be 1.1Æ0.1 ppm.
3
. [c] The amount of tin residues in the product 11a was measured
partial isomerization of crotyl-
Discussion of mechanism: From these different results,
whatever the natures of the functional groups borne either
by the supported allyltin reagent or by the aldehyde sub-
strate, it appears that supported allyltins, in the presence of
appropriate Lewis acids, can act as efficient allylation re-
agents. Furthermore, it is noteworthy that experimental con-
tributyltin into the less stable,
but more reactive, 3-tributylstannyl-but-1-ene before addi-
tion to the aldehyde (Lewis acids facilitate this equilibrium).
It is of interest to note that opposite stereochemical trends
were observed by Loh in allylation reactions performed
with crotyl bromide and metals in aqueous media (an anti
preference being the main stereochemical trend for the
branched isomers, while linear ones were obtained with high
ditions involving cerium
A
H
R
U
G
A
H
R
U
patible for applications in automated parallel synthesis. At
this level, the question might be the real usefulness of the
supported allyltins, since the effective species might be allyl-
cerium or allylindium reagents resulting from a transmetal-
[
37]
E stereoselectivity). In a very closely related area, reac-
tions between crotyltributyltins and aldehydes in the pres-
ence of carboxylic acids were recently reported by Zhao and
Li. In this case, a strong preference for the linear isomer 27
was observed, but the proposed mechanism can hardly ac-
[12,35]
lation reaction.
Since allylcerium or allylindium species should react
[35]
[38]
through a six-membered cyclic transition state, in contrast
with an open, acyclic transition state when allyltriorganotins
are allowed to react with the aldehyde/Lewis acid com-
count for the very high Z stereoselectivity.
In summary, our stereochemical results are consistent
with a mechanism in which the effective allylating species
should be allyltins, which should react with aldehydes linked
to BF , InCl , or InBr . It suggests that these salts are acting
[36]
plex, the stereochemistry of the reactions involving simple
g-substituted allylmetals should be indicative of the nature
3
3
3
mainly (or exclusively)as
simple Lewis acids (without
transmetalation of the organo-
tin reagent)under our experi-
mental conditions (those used
for studies involving supported
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F. Zammattio, J.-P. Quintard et al.
1
19
allyltins). The mechanistic aspects of these reactions, which
can be strongly affected by the natures of the solvent and
the additives and more generally by the experimental condi-
tions, will be discussed in detail elsewhere.
Sn MAS-NMR spectra of these resins only showed very
ill-defined noisy signals, so the clear identification of the ex-
pected distannoxane-type species was impossible, an obser-
vation consistent with previous reports in the literature.
[40]
In spite of this, the obtained resin was amenable to regener-
ation (vide infra).
Investigations of Sn andCe contamination in the obtained
1
3
1
homoallylic alcohols: The C NMR and H NMR spectra of
the isolated homoallylic alcohols indicated no meaningful
contamination by organotin residues. This observation was
subsequently confirmed by ICP-MS analysis, which showed
low or insignificant tin contamination (<5 ppm). Moreover,
cerium residues were also quantified as below 1 ppm by ICP
emission analysis of the crude homoallylic alcohols when
this Lewis acid was used as a promoter. At this stage, com-
plete validation of the method required the potential to re-
cycle the recovered polymer-supported tin reagents at the
end of the allylation reactions. For this purpose, the resin
particles recovered at the end of the three different allyla-
tion processes were washed with THF and absolute ethanol,
dried under vacuum, and characterized by IR and
Reuse of the organotin resins: The three different types of
resins recovered after the allylation reactions were regener-
ated and reused. The recovered resins were allylated by the
previously described one-pot procedure with allyl bromide
and Zn (vide supra, Scheme 3)or by treatment with allyl-
magnesium bromide, with the regeneration of the polymer-
supported allyltin reagents 1a–d being checked by
1
19
Sn MAS-NMR spectroscopy.
It is worth noting that zinc or/and magnesium salts are re-
tained in the polymeric matrix, together with oxygenated
solvents, but without prohibitive effects on the regeneration
and further use of supported allyltins (cf. Experimental Sec-
tion). Accordingly, the reactivities of the regenerated resins
1a–d were evaluated in the allylation of benzaldehyde.
Table 6 shows the functional group capacity values, together
119
Sn MAS-NMR spectroscopy before being regenerated
1
19
and reused. As an example, in the Sn MAS-NMR spectra
of the resins recovered at the end of the reactions promoted
either by CeCl ·7H O/NaI (10%)or InBr 3, the signals at
3
2
Table 6. Functional group capacity values and yields of homoallylic alco-
hols.
+
147 and +133 ppm are indicative of the regeneration of
[39]
the polymer-supported tin halides 5b and 5c (Figure 1).
[a]
[c]
[d]
Run Yield
%]
%
Sn
Tin loading
Tin content in 9a
[ppm]
That these organotin halides had been isolated was further
evidenced by elemental analysis (cf: Experimental Section).
In the case of the BF ·OEt -promoted allylation reactions,
[b]
À1
[
[mmolg
]
1
2
3
4
5
95
95
94
92
90
18.1
17.4
17.5
17.2
18.1
1.53
1.47
1.47
1.45
1.53
3.8Æ0.2
3.6Æ0.3
2.9Æ0.2
3.3Æ0.2
1.7Æ0.2
3
2
the recovered resins were less easily characterized and the
[
a] Isolated yield of 1-phenyl-but-3-en-1-ol (9a). [b] Percentage of tin in
the regenerated polymer 1a determined by elemental analysis [c] Tin
loading on the regenerated polymer 1a. [d] Tin content in the final prod-
ucts 9a determined by ICP-MS analysis.
with the yields of homoallylic alcohols obtained after one to
five regeneration cycles with resin 1a. The recycled resin 1a
gave similarly high reactivity in subsequent reactions. For
1
19
each cycle, we recorded
Sn MAS-NMR spectra before
and after reaction in order to check the recyclability, and in
all cases the regenerated allyltin 1a displayed the same spec-
trum as the first generated allyltin 1a, with a unique signal
at À18.5 ppm (see Figure 1b). Similarly, after the reactions
the recovered resins each displayed a unique signal indica-
tive of a tin halide moiety (SnÀBr or SnÀCl depending on
1
19
Figure 1. Solid-state Sn MAS-NMR spectra of polymer-supported orga-
the nature of the Lewis acid used; see Figure 1c and d). We
additionally checked the presence of tin residues in the final
products by ICP-MS and found insignificant tin contamina-
tion (between d=3.8 and 1.7 ppm). These results are in
agreement with the constant tin loading in polymer, showing
that the loss of tin from the supported reagent 1a, as well as
the metal leaching, was negligible after five runs.
notin reagents. a)Polymer 5a, d(Sn) = +80 ppm. b)Polymer 1a, d(Sn)
=
À18.5 ppm, obtained from 5a. c)Polymer 5b obtained after the first
allylstannation mediated by CeCl ·7H O/NaI (10%), d(Sn)
147 ppm. d)Polymer 5c obtained after the InBr -mediated allylstanna-
3
2
=
+
3
tion, d(Sn) = +133 ppm. e)Polymer 1a obtained after the first recycling
from 5b with allylmagnesium chloride, d(Sn) = À18.5 ppm. f)Polymer
5
3 2
b obtained after the second allylstannation mediated by CeCl ·7H O/
NaI (10%), d(Sn) = +147 ppm. g)Polymer 1a obtained after the second
recycling from 5b with allylmagnesium chloride, d(Sn) = À18.5 ppm.
h)Polymer 1a obtained after the fourth recycling from 5b with allylmag-
nesium chloride, d(Sn) = À18.5 ppm.
6822
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 6816 – 6828

Allyltin Reagents on Solid Support
FULL PAPER
out-of-plane aromatic C
ÀH bending bands, 759, 698 (monosubstituted ar-
omatic rings).
Conclusion
Elemental analyses were carried out by the CNRS Analysis Central Lab-
oratory, Vernaison, France, on a Perkin–Elmer 2400 analyzer.
We have developed an efficient method for the synthesis of
polymer-bounded functionalized tin reagents 1a–d. This
method offers several advantages, including mild reaction
conditions, in situ formation of allylzincs, and good loadings
X-ray energy-dispersive spectrometry (EDS)measurements were carried
out on a PGT spectrometer (Prism model)with use of appropriate stand-
ards in view of quantitative measurements.
À1
in allyltins (1.1 to 1.4 mmolg ). We have also shown the
ICP-MS analyses were performed on VG Elemental PQ Excell apparatus
(Thermo-Electron GB). The ICP was operated at 1350 W and all parame-
ters were optimized to obtain the maximum sensitivity (ions optics, flow
rates, glassware position …). Nebulization was performed with a Mein-
usefulness of these new polymer-supported organotin re-
agents 1a–d for the allylstannation of aldehydes. The mech-
anism aspects of the allylation of aldehydes with polymer-
supported allyltins 1a–d in the presence of cerium or indium
salts were briefly explored through an extrapolation of the
reaction involving crotyltri-n-butyltin. The experimental al-
lylation procedure with use of polymer-supported allyltins in
the presence of either CeCl ·7H O/NaI (10%)or InX (X =
À1
hart nebulizer working at 1 mLmin . A fully quantified analytical
method was set up, using eight points of calibration between 0 and 1 ppb
of tin. The material was dissolved in a mixture (5 mL)of nitric acid (2%)
and acetone and interferences of the matrix were studied to correct the
analytical results. No internal reference was used but the stability over
time was checked every five samples, and memory effect was also
checked between each sample.
3
2
3
Br, Cl)is reasonably convenient and environmentally friend-
ly, since only a negligible amount of tin remains in the final
products (<5 ppm). Moreover, the recovered resins can be
regenerated and reused several times without notable loss
of activity. Accordingly, these new immobilized reagents are
particularly adaptable to automated parallel synthesis with-
out significant tin contamination, allowing access to libraries
of homoallylic alcohols, a strategy potentially extendable to
other fine chemicals.
Synthesis
[
9a]
Synthesis of poly(4-chlorobutyl)styrene: TMEDA (8.7 mL, 57.7 mmol)
and a solution of n-butyllithium (2.5m in hexanes, 27.7 mL, 69.2 mmol)
were added successively, under argon, to a suspension of Amberlite
XE 305 (6.0 g)in dry cyclohexane (15 mL.) The reaction mixture was
heated at 658C for 4 h. The resin was then washed under argon with dry
cyclohexane (8”20 mL), and this procedure (TMEDA, n-butyllithium)
was repeated once. The resulting orange lithiated polymer was then
washed under argon with dry THF (12”20 mL). 1-Bromo-4-chlorobutane
(
7.9 mL, 68.6 mmol)was added, at 0 8C under argon, to the lithiated poly-
mer suspension in dry THF (50 mL). The mixture was stirred at room
temperature for 18 h and the resulting polymer was then successively
2
washed with a THF/H O mixture (1:1 v/v, 40 mL), THF (6”40 mL), and
Experimental Section
absolute ethanol (4”40 mL)and dried under vacuum (0.5 mbar)at 60 8C
for 5 h. Polymer 1 was obtained as a white resin (7.8 g)and was found to
General
À1
contain 2.21 mmol of CÀClg : IR (KBr): n˜ = 3082, 3059, 3025, 2921,
With the exception of di- or tributyltin derivatives, which were obtained
from Crompton, the other starting materials were purchased from Al-
drich or Acros and were used without further purification. Amberlite
XE-305 was a Rohm and Haas product and was purchased from Inter-
chim. Dibutylphenyltin hydride was prepared by a described proce-
2850, 1942, 1870, 1802, 1719, 1601, 1586, 1493, 1452, 1028, 759, 698, 650,
À1
539 cm ; elemental analysis (%)found: C 82.59, H 7.72, Cl 7.86, Br 0.43.
[9a]
Synthesis of poly[4-(dibutylphenylstannyl)butyl]styrene:
Dibutylphe-
nyltin hydride (8.62 g, 27.7 mmol)was slowly added, at 0 8C under argon,
to a solution of lithium diisopropylamide (30.5 mmol)in dry THF. The
resulting mixture was stirred for 1 h at 08C and subsequently added at
[
41]
dure. Diethyl ether and THF were distilled over sodium/benzophenone
ketyl and cyclohexane was distilled over calcium hydride.
0
8C under argon to the dry poly(4-chlorobutyl)styrene (6.0 g). The mix-
Melting points (uncorrected)were determined on a C. Reichert micro-
scope apparatus.
ture was allowed to warm up to room temperature and stirred for 18 h.
The resulting polymer was successively washed with a mixture of THF/
H O (1:1 v/v, 60 mL), THF (6”60 mL), and absolute ethanol (4”60 mL)
2
1
13
H and C NMR spectra were recorded on a Bruker Avance 300 spec-
1
13
trometer operating at 300 MHz for H and 75.5 MHz for C in CDCl
3
and dried under vacuum (0.5 mbar)at 60 8C for 5 h. Poly[4-(dibutylphe-
solution at 258C. Chemical shifts (d)are expressed in ppm downfield of
tetramethylsilane (TMS), used as internal standard, and coupling con-
stants (J)are expressed in Hertz.
nylstannyl)butyl]styrene was obtained as a white resin (10.4 g) and was
À1 119
found to contain 1.33 mmol of Sng
IR (KBr): n˜ = 3082, 3059, 3025, 2921, 2850, 1942, 1870, 1802, 1719, 1601,
:
Sn MAS-NMR: d = À43.4 ppm;
À1
1
586, 1493, 1452, 1073, 1028, 759, 726, 698 cm ; elemental analysis (%)
Solid-state MAS-NMR experiments were performed at room tempera-
ture with a Bruker Avance 500 spectrometer operating at 186.5 MHz for
found: C 74.87, H 7.12, Sn 15.76, Cl <0.20.
1
19
119
[9a]
Sn with a 4 mm double-bearing Bruker probehead. Sn MAS spectra
Synthesis of poly[4-(dibutyliodostannyl)butyl]styrene 5a: A solution of
iodine (3.81 g, 15.0 mmol)in absolute ethanol (50 mL)was added to the
poly[4-(dibutylphenylstannyl)butyl]styrene (10.0 g) and the resulting mix-
ture was stirred at 608C for 18 h in the dark. The polymer was successive-
ly washed with a mixture of THF/aqueous Na S O (1:1 v/v, 60 mL), THF
1
[42]
were acquired with H TPPM decoupling
during acquisition and a
MAS frequency of 10 kHz. The repetition time was set to 20 s for quanti-
1
19Sn
tative purposes since
1
T were measured to be of the order of 3 s for
all kind of Sn cores. In a control experiment performed on a mixture of
2
2
3
two different Sn species (SnÀX, SnÀC), with a repetition time of 300 s no
(6”60 mL), and absolute ethanol (4”60 mL) and dried under vacuum
modification of the integrations was observed relative to spectra obtained
(0.5 mbar)at 60 8C for 5 h. Polymer 5a was obtained as a pale yellow
À1
with a repetition time of 20 s. Spectra were referenced to Me
4
Sn with use
resin (10.7 g)and was found to contain 1.16 mmol of Sn ÀIg
:
[
30]
119
of Ph
Mass spectra were recorded on a HP 5989 A spectrometer (EI, 70 eV or/
and CI, NH )in direct introduction mode.
4
Sn as a secondary reference (d=À121.15 ppm).
Sn MAS-NMR: d = +80.5 ppm; IR (KBr): n˜ = 3082, 3059, 3025,
2921, 2850, 1942, 1870, 1802, 1719, 1601, 1586, 1493, 1452, 1073, 1028,
À1
759, 698 cm ; elemental analysis (%)found: C 63.22, H 7.00, Sn 14.30, I
3
1
4.78.
IR spectra were recorded on a Bruker Vector 22 FT-IR spectrometer
from dry KBr pellets (400 mg)with substance (4 mg)or polymer (10 mg).
General procedure for the synthesis of polymer-supported allyltin re-
À1 [29a]
Polystyrene bands (cm ):
aromatic CÀH stretchings, 3082, 3059, 3025;
agents 1a–dwith isolatedallylzinc bromi de reagents : A solution of allyl-
[
43]
aliphatic CÀH stretchings, 2921, 2850; weak overtone bands, 1942, 1870,
zinc bromide
(7.0 mmol)was added to a suspension of polymer 5a
1
1
802, 1719 (monosubstituted aromatic rings); aromatic CÀC stretchings:
(3.0 g, 3.48 mmol)in dry THF (10 mL)and the resulting mixture was stir-
red at 458C for 18 h. The polymer 1a was successively washed with a
601, 1586, 1493, 1452; weak in-plane aromatic CÀH bending band: 1028;
Chem. Eur. J. 2006, 12, 6816 – 6828
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6823

F. Zammattio, J.-P. Quintard et al.
mixture of THF/aqueous NH
4
Cl (1:1 v/v, 30 mL), THF (6”30 mL), and
General procedure for the allylstannation of aldehydes promoted by
absolute ethanol (4”30 mL)and dried under vacuum (0.5 mbar)at 60 8C
for 5 h. The same procedure was used for 1b, 1c, and 1d, in the two last
cases with preparation of the functional allylzinc bromide, which must be
CeCl
and NaI (0.1 mmol)were successively added to a suspension of polymer
1a,b (1.0 g, 1.4 mmol)in CH CN. The reaction mixture was stirred at
608C for 24 h and was then quenched with HCl (0.1m, 10 mL). The poly-
mer was filtered and was washed first with diethyl ether (6”30 mL)and
then with THF (6”30 mL). The filtrate was extracted with diethyl ether
3 2 3 2
·7H O/NaI (10%): Aldehyde (1.0 mmol), CeCl ·7H O (1.0 mmol),
3
[
28]
done at 198C.
General procedure for the synthesis of polymer-supported allyltin re-
agents 1a–din a Barbier mo de : Allyl bromide (17.4 mmol)was added to
a suspension of polymer 5a (3.0 g, 3.48 mmol)and zinc powder (30 mesh,
4
and washed with brine (50 mL), dried over MgSO , and concentrated
under vacuum. The crude product was purified by chromatography on
silica gel. Otherwise, the resulting polymer was washed with absolute
ethanol (4”40 mL)and dried under vacuum (0.5 mbar)at 60 8C for 5 h
before being reused. Polymer 5b was obtained as a white resin and was
1
4
7.4 mmol)in dry THF (10 mL ), and the resulting mixture was stirred at
58C for 18 h. The polymer was successively washed with a mixture of
4
THF/aqueous NH Cl (1:1 v/v, 30 mL), THF (6”30 mL), and absolute
ethanol (4”30 mL)and dried under vacuum (0.5 mbar)at 60 8C for 5 h.
À1
119
found to contain 1.36 mmol of SnÀClg
147 ppm; elemental analysis (%)found: C 67.64, H 7.44, Sn 16.12, Cl
.01.
.
Sn MAS-NMR: d =
Polymer 1a: Polymer 1a was obtained as a white resin and was found to
+
À1
119
contain 1.41 mmol of Sng
(
:
Sn MAS-NMR: d
=
À18.5 ppm; IR
6
À1
KBr): n˜ = 1622 cm ; elemental analysis (%)found: C 70.06, H 8.41, Sn
Characterization of homoallylic alcohols: All compounds were obtained
by the above general procedure for the allylstannation of aldehydes pro-
moted by CeCl ·7H O/NaI (10%). In the EI-MS spectra, the fragmenta-
3 2
tion scheme is mainly governed by benzylic scission, followed by minor
1
6.68, I <0.20.
Polymer 1b: Polymer 1b was obtained as a white resin and was found to
À1
119
contain 1.11 mmol of Sng
(
:
Sn MAS-NMR: d
=
À17.1 ppm; IR
À1
KBr): n˜ = 1629 cm ; elemental analysis (%)found: C 71.82, H 8.50, Sn
subsequent fragmentations including extrusion of carbon monoxide from
1
3.22, I <0.20.
[44]
the hydroxytropylium ion,
while CI-MS spectra mainly exhibit quasi
+
+
Polymer 1c: Polymer 1c was obtained as a white resin and was found to
molecular ions for [M+NH
4
]
2 4
and for [MÀH O+NH ] .
À1
119
contain 1.23 mmol of Sng
(
7
:
Sn MAS-NMR: d
KBr): n˜ = 1710, 1612 cm ; elemental analysis (%)found: C 72.41, H
.70, Sn 14.56, I 0.62.
=
À12.1 ppm; IR
[45]
1
-Phenylbut-3-en-1-ol (9a): Compound 9a was obtained from benzal-
À1
dehyde (1.0 mmol)and polymer 1a as a colorless oil (141 mg, 95%)after
purification by flash chromatography (petroleum ether/ethyl acetate
1
Polymer 1d: Polymer 1d was obtained as a yellow resin and was found
88:12, R = 0.16); H NMR: d = 2.02 (d, J = 3.3 Hz, 1H), 2.44–2.58 (m,
f
À1 119
to contain 1.19 mmol of Sng
(
:
Sn MAS-NMR: d = À9.5 ppm; IR
2H), 4.72–4.75 (ddd, J = 3.3, 5.4, 8.1 Hz, 1H), 5.14–5.21 (m, 2H), 5.82
À1
13
KBr): n˜ = 2200 cm ; elemental analysis (%)found: C 72.05, H 7.71, Sn
(ddt, J = 7.1, 10.2, 17.2 Hz, 1H), 7.24–7.37 (m, 5H) ppm; C NMR: d =
1
4.09, N 1.66, I 0.56.
43.8, 73.3, 118.3, 125.8 (2”C), 127.5, 128.4 (2”C), 134.6, 143.9 ppm; IR
It is worth noting that the sums of the mass percentages turn out to be
around 95% for the four polymers. This problem does not appear to be
due to bad evaluation of tin since the N/Sn ratio is good in 1d. Another
possibility might be the presence of oxygenated solvents or of zinc salts
remaining in the matrix. In order to make a broad evaluation of these hy-
potheses, EDS measurements were performed on 1a and 1c. The given
results are each the average of three measurements. In the case of 1a
(KBr): n˜ = 3390, 3076, 3065, 3030, 2925, 2856, 1641, 1600, 1493, 1464,
1048, 915, 756, 699 cm ; MS (EI, 70 eV): m/z (relative intensity): 107
À1
(100), 79 (68), 77 (31), 51 (9).
[
46]
1-(4-Bromophenyl)but-3-en-1-ol (10a):
Compound 10a was obtained
from 4-bromobenzaldehyde (1.0 mmol)and polymer 1a as a colorless oil
(225 mg, 99%)after purification by flash chromatography (petroleum
1
ether/ethyl acetate 88:12, Rf = 0.26); H NMR: d = 2.27 (brs, 1H),
(
obtained from 5a with allylmagnesium chloride), an evaluation of tin,
2.38–2.53 (m, 2H), 4.67 (dd, J = 5.7, 7.5 Hz, 1H), 5.12–5.18 (m, 2H),
5.69–5.83 (m, 1H), 7.21 and 7.46 (AA’BB’ system, J = 8.1 Hz, 4H)ppm;
C NMR: d = 43.8, 72.6, 118.9, 121.3, 127.6 (2”C), 131.5 (2”C), 134.0,
halogens, magnesium, zinc, carbon, and oxygen afforded the following
values (normalized to 100% in weight, italic numbers are under the
limits of the precision of the measurement): Sn (12.55), Br (0.13) , I
1
3
142.9 ppm; MS (EI, 70 eV): m/z (relative intensity): 228/226 (1), 211/209
(
0.06), Cl (3.02), Mg (1.10), Zn (0.17), C (76.94), O (6.02). Similar meas-
(1), 187/185 (92), 159/157 (25), 105 (8), 78 (54), 77 (100), 51 (21), 41 (11),
urements carried out on 1c (obtained from recycled 5b upon treatment
with 8c and Zn) afforded the following set of values: Sn (9.99), Br (0.19),
I (0.11), Cl (0.30), Mg (0.03), Zn (0.25), C (82.0), 0 (7.12). In spite of the
unavoidable uncertainty in the low mass fractions of zinc, magnesium,
and the halogens, they are in satisfactory agreement with the presence of
residual magnesium or zinc dihalides, since the molar ratio of zinc or
magnesium to halogen is roughly 1 to 2.
39 (18); MS (CI, NH
(100), 211/209 (13).
3
): m/z (relative intensity): 246/244 (3), 228/226
[45]
1
-(4-Nitrophenyl)but-3-en-1-ol (11a):
Compound 11a was obtained
from 4-nitro-benzaldehyde (1.0 mmol)and polymer 1a as a brown oil
188 mg, 97%)after purification by flash chromatography (petroleum
(
1
ether/ethyl acetate 85:15, R
f
= 0.15); H NMR: d = 2.46–2.59 (m, 3H),
4
.85 (dd, J = 4.8, 8.1 Hz, 1H), 5.13–5.19 (m, 2H), 5.70–5.84 (m, 1H),
1
3
The excess of oxygen (about 6% in 1a and 4.4% in 1c with allowance
for the presence of the ester function)can reasonably be assigned to re-
tained oxygenated solvents in the matrix. Although needing to be
checked in a more efficient way, it is worth noting that the presence of
magnesium or zinc salts, as well as that of oxygenated solvents in the
matrix, is not prohibitive either for the regeneration of the grafted allyl-
tins or for their subsequent treatment with aldehydes, due to the fact that
allylation is usually performed in the presence of Lewis acids.
7.51 and 8.17 (AA’BB’ system, J = 9.0 Hz, 4H)ppm; C NMR d =
43.9, 72.1, 119.6, 123.6 (2”C), 126.6 (2”C), 133.2, 147.2, 151.2 ppm; MS
(EI, 70 eV): m/z (relative intensity): 152 (100), 124 (3), 122 (12), 106
(16), 105 (16), 94 (20), 78 (20), 77 (20), 51 (14), 41 (8), 39 (12); MS (CI,
3
NH ): m/z (relative intensity): 228 (5), 211 (100), 146 (24).
[
46]
1-(4-Methoxyphenyl)but-3-en-1-ol (12a): Compound 12a was obtained
from 4-methoxybenzaldehyde (1.0 mmol)and polymer 1a as a colorless
oil (146 mg, 88%)after purification by flash chromatography (petroleum
1
General procedure for the BF
hydes: Benzaldehyde (1.7 mmol)and a solution of BF
were added dropwise at À788C, under argon to a suspension of polymer
a–c (1.3 g, 1.8 mmol)in dry CH Cl . The reaction mixture was stirred at
À788C for 2 h and was then quenched with a THF/H O mixture (1:1 v/v).
The polymer was filtered and was washed first with diethyl ether (6”
0 mL)and then with THF (6”40 mL .) The filtrate was extracted with
diethyl ether, washed with brine (50 mL), dried over MgSO , and concen-
3
·OEt
2
-promotedallylstannation of al de -
ether/ethyl acetate 85:15, R
f
= 0.40); H NMR: d = 2.32 (brs, 1H), 2.47
·OEt (6.8 mmol)
2
(t, J = 6.9 Hz, 2H), 3.77 (s, 3H), 4.64 (t, J = 6.9 Hz, 1H), 5.08–5.15 (m,
2H), 5.77 (ddt, J = 17.4, 10.2, 6.9 Hz, 1H), 6.86 and 7.25 (AA’BB’
3
1
3
system, 4H)ppm; C NMR: d = 43.6, 55.1, 72.9, 113.7 (2”C), 118.0,
27.0 (2”C), 134.6, 136.0, 158.9 ppm; MS (CI, NH ): m/z (relative inten-
1
2
2
1
3
2
sity): 178 (2), 161 (100).
[
47]
4
1-(2-Tosylaminophenyl)but-3-en-1-ol (13a):
tained from 2-tosylaminobenzaldehyde (1.0 mmol)and polymer 1a as a
Compound 13a was ob-
4
trated under vacuum. The crude product was purified by chromatography
on silica gel. The resulting polymer, on the other hand, was washed with
absolute ethanol (4”40 mL)and dried under vacuum (0.5 mbar)at 60 8C
for 5 h before being reused in reaction with allylzinc reagents.
white solid (264 mg, 83%)after purification by flash chromatography
(petroleum ether/ethyl acetate 85:15, Rf = 0.21); H NMR: d = 2.28–
2.34 (m, 2H), 2.37 (s, 3H), 4.64 (dd, J = 6.0, 8.1 Hz, 1H), 5.03–5.14 (m,
2H), 5.57–5.71 (m, 1H), 7.04 (d, J = 8.1 Hz, 2H), 7.17–7.25 (m, 3H),
1
6824
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 6816 – 6828

Allyltin Reagents on Solid Support
FULL PAPER
1
3
7
2
.47 (d, J = 8.4 Hz, 1H), 7.70 (d, J = 8.1 Hz, 2H)ppm; C NMR: d =
1.5, 41.3, 73.4, 119.3, 121.8, 124.5, 127.1 (2”C), 127.8, 128.6, 129.6 (2”
1-(6-Bromopyridin-2-yl)but-3-en-1-ol (20a): Compound 20a was obtained
from 6-bromopyridine-2-carboxaldehyde (1.0 mmol)and polymer 1a as a
C), 132.0, 133.7, 135.8, 137.0, 143.8 ppm; MS (EI, 70 eV): m/z (relative in-
tensity): 317 (5), 300, (5), 276 (27), 248 (14), 156 (20), 155 (56), 145 (29),
colorless oil (194 mg, 85%)after purification by flash chromatography
1
(CH
2
Cl
2
, R
f
= 0.20); H NMR: d = 2.41–2.69 (m, 2H), 3.31 (d, J =
1
(
44 (31), 121 (17), 120 (17), 93 (37), 92 (20), 91 (100), 65 (33), 41 (10), 39
13).
-(3-Bromophenyl)but-3-en-1-ol (14a):
from 3-bromobenzaldehyde (1.0 mmol)and polymer 1a as a colorless oil
194 mg, 85%)after purification by flash chromatography (petroleum
5.4 Hz, 1H), 4.74–4.80 (m, 1H), 5.09–5.16 (m, 2H), 5.73–5.87 (m, 1H),
7.30 (d, J = 7.8 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H), 7.54 (t, J = 7.8 Hz,
1
3
[
48]
1H)ppm; C NMR: d = 42.6, 72.3, 118.7, 119.2, 126.7, 133.7, 139.0,
1
Compound 14a was obtained
1
41.2, 163.6 ppm; MS (EI, 70 eV): m/z (relative intensity): 229/227 (3),
1
88/186 (100), 158/156 (11), 106 (35), 79 (11), 78 (47), 51 (23), 41 (7), 39
(
1
(11); elemental analysis calcd (%) for C
9
H10BrNO (228.09): C 47.39, H
ether/ethyl acetate 9:1, R
f
= 0.26); H NMR: d = 2.18 (brs, 1H), 2.39–
4
.42, Br 35.03, N 6.14, O 7.01; found: C 47.03, H 4.21, Br 35.09, N 6.33.
2
5
.56 (m, 2H), 4.69 (dd, J = 4.8, 7.8 Hz, 1H), 5.15–5.20 (m, 2H), 5.71–
[
52]
1
-(Quinolin-3-yl)but-3-en-1-ol (21a):
Compound 21a was obtained
.85 (m, 1H), 7.18–7.28 (m, 2H), 7.38–7.42 (m, 1H), 7.52 (s, 1H) ppm;
C NMR: d = 43.8, 72.5, 119.0, 122.6, 124.4, 128.9, 130.0, 130.6, 133.9,
46.2 ppm; MS (EI, 70 eV): m/z (relative intensity): 187/185 (83), 159/157
1
3
from quinoline-3-carboxaldehyde (1.0 mmol)and polymer 1a as a yellow
oil (136 mg, 68%)after purification by flash chromatography (petroleum
1
1
ether/ethyl acetate 6:4, R
f
= 0.20); H NMR: d = 2.47 (brs, 1H), 2.58–
(
38), 78 (46), 77 (100), 51 (26), 41 (10), 39 (17); MS (CI, NH
3
): m/z (rela-
2
.72 (m, 2H), 4.99 (dd, J = 7.5, 5.4 Hz, 1H), 5.18–5.24 (m, 2H), 5.77–
tive intensity): 246/244 (24), 228/226 (100).
[
49]
5.91 (m, 1H), 7.55 (dt, J = 8.1, 0.9 Hz, 1H), 7.70 (dt, J = 8.1, 1.5 Hz,
1
-(2,6-Dichlorophenyl)-but-3-en-1-ol (15a):
Compound 15a was ob-
1
2
1
1
H), 7.82 (d, J = 8.1 Hz, 1H), 8.12 (d, J = 8.1 Hz, 1H), 8.15 (d, J =
.1 Hz, 1H), 8.89 (d, J = 2.1 Hz, 1H)ppm; C NMR: d = 43.8, 71.2,
tained from 2,6-dichloro-benzaldehyde (1.0 mmol)and polymer 1a as a
colorless oil (201 mg, 93%)after purification by flash chromatography
1
3
19.3, 126.8, 127.8 (2”C), 129.1, 129.3, 132.7, 133.6, 136.5, 147.6,
1
(
petroleum ether/ethyl acetate 9:1, R
f
= 0.40); H NMR: d = 2.68 (q, J
À1
49.3 ppm; IR (KBr): n˜ = 3138, 2943, 1636 cm ; MS (EI, 70 eV): m/z
=
6.6 Hz, 1H), 2.84 (q, J = 6.6 Hz, 1H), 2.92 (d, J = 9.3 Hz, 1H), 5.07–
.16 (m, 2H), 5.49 (dt, J = 6.6, 9.3 Hz, 1H), 5.77–5.91 (m, 1H), 7.13 (t, J
(
(
relative intensity): 199 (1), 158 (100), 130 (36), 103 (11), 77 (13); MS
CI, NH ): m/z (relative intensity): 200 (100), 182 (5), 158 (71) ppm.
-(Furan-2-yl)but-3-en-1-ol (22a): Compound 22a was obtained from
furan-2-carboxaldehyde (1.0 mmol)and polymer 1a as a colorless oil
120 mg, 87%)after purification by flash chromatography (petroleum
5
=
1
3
3
8.1 Hz, 1H), 7.29 (d, J = 8.1 Hz, 2H)ppm; C NMR: d = 40.0, 71.4,
[53]
1
1
7
6
18.1, 128.9, 129.4 (2”C), 133.8, 134.3 (2”C), 137.2 ppm; MS (EI,
0 eV): m/z (relative intensity): 179/177/175 (10/60/100), 151/149/147 (1/4/
(
3
), 141/139 (3/10), 113/111 (12/41), 75 (32), 41 (6), 39 (10); MS (CI, NH ):
1
ether/ethyl acetate 9:1, R
2
1
f
= 0.20); H NMR: d = 2.20 (brs, 1H), 2.57–
.64 (m, 2H), 4.74 (t, J = 6.3 Hz, 1H), 5.12–5.21 (m, 2H), 5.73–5.87 (m,
H), 6.25 (d, J = 3.3 Hz, 1H), 6.33 (dd, J = 3.3, 1.8 Hz, 1H), 7.37 (d, J
m/z (relative intensity): 238/236/234 (10/63/100), 220/218/216 (2/12/19).
[
50]
1
-(3,4,5-Trimethoxyphenyl)but-3-en-1-ol (16a): Compound 16a was ob-
tained from 3,4,5-trimethoxy-benzaldehyde (1.0 mmol)and polymer 1a
as a colorless oil (177 mg, 74%)after purification by flash chromatogra-
phy (CH
2
1
13
=
1.8 Hz, 1H)ppm; C NMR: d = 40.1, 66.9, 106.1, 110.1, 118.6, 133.7,
42.0, 156.0 ppm; MS (EI, 70 eV): m/z (relative intensity): 138 (2), 97
100), 69 (14), 41 (32), 39 (18).
-(Thiophen-2-yl)but-3-en-1-ol (23a):
from thiophene-2-carboxaldehyde (1.0 mmol)and polymer 1a as
yellow oil (137 mg, 89%)after purification by flash chromatography (pe-
1
(
1
2
Cl
2
/ethanol 98:2, R
f
=
0.13); H NMR: d
=
2.11 (d, J
=
.7 Hz, 1H), 2.45–2.52 (m, 2H), 3.83 (s, 3H), 3.87 (6H, s), 4.64–4.69 (m,
[
53]
1
Compound 23a was obtained
13
H), 5.14–5.23 (m, 2H), 5.75–5.87 (m, 1H), 6.59 (s, 2H) ppm; C NMR:
a
d = 43.9, 56.1, 60.8, 73.4, 102.6 (2”C), 118.5, 134.5, 137.1, 139.7, 153.2
(
(
2C)ppm; MS (EI, 70 eV ): m/z (relative intensity): 238 (10), 220 (4), 197
100), 169 (72), 154 (32), 139 (15), 138 (52).
1
troleum ether/ethyl acetate 92:8, R
H), 2.59–2.65 (m, 2H), 4.95–5.00 (m, 1H), 5.16–5.23 (m, 2H), 5.77–5.91
m, 1H), 6.98 (d, J 3.0 Hz, 2H), 7.26 (t, J 3.0 Hz, 1H)ppm;
C NMR: d = 43.5, 69.2, 118.4, 123.6, 124.4, 126.4, 133.8, 147.7 ppm; MS
EI, 70 eV): m/z (relative intensity): 154 (2), 113 (100), 85 (38), 45 (16),
1 (8), 39 (12).
Dec-1-en-4-ol (24a): Compound 24a was obtained from heptaldehyde
1.0 mmol)and polymer 1a as a colorless oil (128 mg, 82%)after purifi-
cation by flash chromatography (petroleum ether/ethyl acetate 9:1, R
f
= 0.20); H NMR: d = 2.56 (brs,
1
[
51]
1
-(4-Dimethylaminophenyl)-but-3-en-1-ol (17a):
Compound 17a was
(
=
=
obtained from 4-dimethylamino-benzaldehyde (1.0 mmol)and polymer
a as a yellow oil (147 mg, 77%)after purification by flash chromatogra-
13
1
(
4
1
phy (petroleum ether/ethyl acetate 8:2, R
f
= 0.24); H NMR: d = 2.49–
.60 (m, 2H), 2.76 (s, 1H), 2.97 (6H, s), 4.63 (t, J = 6.3 Hz, 1H), 5.12–
.21 (m, 2H), 5.78–5.92 (m, 1H), 6.77 and 7.25 (AA’BB’ system, J =
2
5
8
1
[54]
(
1
3
.7 Hz, 4H)ppm; C NMR: d = 40.5 (2”C), 43.2, 73.0, 112.4 (2”C),
17.1, 126.6 (2”C), 132.0, 134.9, 149.8 ppm; MS (EI, 70 eV): m/z (relative
f
=
1
0
.35); H NMR: d = 0.88 (t, J = 6.6 Hz, 3H), 1.22–1.45 (10H, m), 1.63
intensity): 173 (85), 172 (100), 157 (55), 156 (20), 129 (40), 128 (34) ppm;
MS (CI, NH ): m/z (relative intensity): 192 (72), 174 (100), 150 (8).
-(Pyridin-3-yl)but-3-en-1-ol (18a): Compound 18a was obtained from
pyridine-3-carboxaldehyde (1.0 mmol)and polymer 1a as a colorless oil
129 mg, 86%)after purification by flash chromatography (CH Cl /etha-
= 0.31); H NMR: d = 2.38–2.51 (m, 2H), 4.67 (t, J =
.3 Hz, 1H), 4.98–5.04 (m, 2H), 5.13 (brs, 1H), 5.64–5.77 (m, 1H), 7.17
dd, J = 7.8, 4.8 Hz, 1H), 7.65 (ddd, J = 7.8, 1.8, 1.8 Hz, 1H), 8.24 (dd,
(
5
brs, 1H), 2.08–2.34 (m, 2H), 3.63 (brs, 1H), 5.10–5.16 (m, 2H), 5.76–
.86 (m, 1H)ppm; C NMR: d = 14.1, 22.6, 25.6, 29.3, 31.8, 36.8, 41.9,
3
13
[
52]
1
70.7, 118.0, 134.9 ppm; MS (EI, 70 eV): m/z (relative intensity): 115 (13),
97 (37), 69 (13), 55 (100), 43 (25), 41 (21); MS (CI, NH ): m/z (relative
intensity): 174 (100), 156 (4), 97 (18).
3
(
2
2
1
nol 95:5, R
6
(
f
[55]
3
-Methyl-1-phenylbut-3-en-1-ol (9b):
Compound 9b was obtained
1b as colorless oil
146 mg, 90%)after purification by flash chromatography (petroleum
from benzaldehyde (1.0 mmol)and polymer
(
a
1
3
J = 4.8, 1.8 Hz, 1H), 8.31 (d, J = 1.8 Hz, 1H)ppm; C NMR: d = 43.4,
0.7, 118.1, 123.3, 133.8, 133.9, 140.0, 147.2, 147.8 ppm; MS (EI, 70 eV):
m/z (relative intensity): 108 (100), 80 (20), 78 (10), 53 (15); MS (CI,
NH ): m/z (relative intensity): 150 (100), 108 (12).
-(6-Methoxypyridin-3-yl)but-3-en-1-ol 19a:
1
f
ether/ethyl acetate 88:12, R = 0.20); H NMR: d = 1.79 (brs, 3H), 2.18
(
7
d, J = 2.4 Hz, 1H), 2.42 (d, J = 6.6 Hz, 2H), 4.82 (dt, J = 2.4, 6.6 Hz,
13
1
H), 4.87 (brs, 1H), 4.93 (brs, 1H), 7.25–7.33 (m, 5H) ppm; C NMR: d
22.3, 48.4, 71.4, 114.1, 125.8 (2”C), 127.5, 128.4 (2”C), 142.4,
144.1 ppm; MS (EI, 70 eV): m/z (relative intensity): 107 (100), 105 (8), 79
(56), 77 (23), 56 (6), 51 (7); MS (CI, NH ): m/z (relative intensity): 180
3
=
[
52]
1
Compound 19a was ob-
tained from 6-methoxypyridine-3-carboxaldehyde (1.0 mmol)and poly-
3
mer 1a as a colorless oil (158 mg, 88%)after purification by flash chro-
(26), 162 (100), 145 (37) ppm; IR (KBr): n˜ = 3074, 3066, 3030, 2857,
1
À1
matography (CH
2
Cl
2
/ethanol 98:2, R
f
= 0.12); H NMR: d = 2.34 (brs,
2932, 2872, 2856, 1645, 1600, 1494, 1464, 1559, 1055, 891, 756, 700 cm
.
[
56]
1
H), 2.48 (t, J = 6.9 Hz, 2H), 3.91 (s, 3H), 4.67–4.71 (m, 1H), 5.12–5.18
1-(4-Bromophenyl)-3-methylbut-3-en-1-ol (10b):
Compound 10b was
(
m, 2H), 5.70–5.82 (m, 1H), 6.72 (d, J = 8.7 Hz, 1H), 7.59 (dd, J = 8.7,
.4 Hz, 1H), 8.06 (d, J = 2.4 Hz, 1H)ppm; C NMR: d = 43.5, 53.5,
obtained from 4-bromo-benzaldehyde (1.0 mmol)and polymer 1b as a
1
3
2
7
3
white solid (220 mg, 91%)after purification by flash chromatography
1
0.8, 110.8, 118.8, 131.9, 133.9, 136.7, 144.6, 163.8 ppm; IR (KBr): n˜ =
(petroleum ether/ethyl acetate 9:1, Rf = 0.24); H NMR: d = 1.80 (s,
À1
373, 3078, 2945, 1639, 1609, 1574, 1452 cm ; MS (EI, 70 eV): m/z (rela-
3H), 2.16 (d, J = 2.4 Hz, 1H), 2.37–2.39 (m, 2H), 4.75–4.80 (m, 1H),
4.85 (s, 1H), 4.94 (s, 1H), 7.26 and 7.47 (AA’BB’ system, J = 8.4 Hz,
+
tive intensity): 180 [M+H] (8), 138 (100), 110 (4), 95 (11); MS (CI,
NH
1
3
3
): m/z (relative intensity): 180 (100), 138 (7) ppm.
4H)ppm; C NMR: d = 22.3, 48.4, 70.7, 114.5, 121.2, 127.5 (2”C),
Chem. Eur. J. 2006, 12, 6816 – 6828
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6825

F. Zammattio, J.-P. Quintard et al.
1
2
31.5 (2”C), 142.0, 143.0 ppm; MS (EI, 70 eV): m/z (relative intensity):
42/240 (0.5), 225/223 (4), 187/185 (75), 185/183 (23), 159/157 (26), 128
2.76 (ddd, J = 14.1, 4.2, 0.9 Hz, 1H), 3.45 (d, J = 3.3 Hz, 1H), 4.20 (q, J
= 7.2 Hz, 2H), 4.87 (ddd, J = 8, 4.2, 3.3 Hz, 1H), 5.55 (dd, J = 1.5,
0.9 Hz, 1H), 6.22 (d, J = 1.5 Hz, 1H), 7.22 and 7.44 (AA’BB’ system,
4H)ppm; C NMR: d = 14.1, 42.4, 61.1, 72.4, 121.0, 127.4 (2”C), 128.4,
131.3 (2”C), 136.7, 142.9, 167.7 ppm; MS (EI, 70 eV): m/z (relative in-
tensity): 254/252 (11), 185/183 (4), 173 (14), 128 (10), 68 (100), 40 (30);
(
12), 105 (9), 78 (59), 77 (100), 56 (19), 51 (20); MS (CI, NH
3
): m/z (rela-
1
3
tive intensity): 260/258 (4), 242/240 (100), 225/223 (31), 186/184 (10).
[
57]
3
-Methyl-1-(4-nitrophenyl)but-3-en-1-ol 11b: Compound 11b was ob-
tained from 4-nitro-benzaldehyde (0.6 mmol)and polymer 1b as a yellow
solid (114 mg, 92%)after purification by flash chromatography (petro-
leum ether/ethyl acetate 85:15, R
2
MS (CI, NH
3
): m/z (relative intensity): 318/316 (13), 301/299 (25), 283/
1
281 (49), 272/270 (100); elemental analysis calcd (%) for C H BrO
= 0.24); H NMR: d = 1.82 (s, 3H),
13 15
3
f
(
299.16): C 52.19, H 5.05, Br 26.71, O 16.04; found: C 52.24, H 5.17, Br
.32 (brs, 1H), 2.35–2.48 (m, 2H), 4.88–4.94 (m, 2H), 4.99 (s, 1H), 7.56
1
3
26.65.
and 8.21 (AA’BB’ system, J = 8.7 Hz, 4H)ppm; C NMR: d = 22.2,
8.5, 70.4, 115.1, 123.7 (2”C), 126.5 (2”C), 141.4, 147.3, 151.4 ppm; MS
4
Ethyl 4-hydroxy-2-methylene-4-(4-nitrophenyl)butanoate (11c): Com-
pound 11c was obtained from 4-nitrobenzaldehyde (0.5 mmol)and poly-
(
CI, NH
3
): m/z (relative intensity): 225 (100), 160 (26).
[
55]
mer 1c as a colorless oil (122 mg, 92%)after purification by flash chro-
1
-(4-Methoxyphenyl)-3-methylbut-3-en-1-ol 12b:
Compound 12b was
1
matography (petroleum ether/ethyl acetate 8:2, R
f
= 0.21); H NMR: d
obtained from 4-methoxy-benzaldehyde (0.6 mmol)and polymer 1b as a
colorless oil (89 mg, 78%)after purification by flash chromatography
= 0.34); H NMR: d = 1.79 (s,
H), 2.08 (d, J = 1.5 Hz, 1H), 2.40–2.44 (m, 2H), 3.81 (s, 3H), 4.77 (dd,
=
1.30 (t, J = 7.2 Hz, 3H), 2.60 (dd, J = 14.1, 8.1 Hz, 1H), 2.80 (ddd, J
1
= 14.1, 4.2, 0.9 Hz, 1H), 3.48 (d, J = 3.6 Hz, 1H), 4.21 (q, J = 7.2 Hz,
(
petroleum ether/ethyl acetate 85:15, R
f
2
H), 4.98 (ddd, J = 8.1, 4.2, 3.6 Hz, 1H), 5.56 (dd, J = 1.2, 0.9 Hz, 1H),
.22 (d, J = 1.2 Hz, 1H), 7.61 and 8.16 (AA’BB’ system, 4H)ppm;
C NMR: d = 14.1, 42.6, 61.4, 72.3, 123.6 (2”C), 126.5 (2”C), 129.0,
36.3, 147.1, 151.4, 167.9 ppm; MS (EI, 70 eV): m/z (relative intensity):
48 (3), 220 (6), 152 (8), 128 (10), 114 (66), 86 (52), 77 (19), 69 (22), 68
3
6
J = 8.1, 5.7 Hz, 1H), 4.85 (d, J = 0.9 Hz, 1H), 4.91 (d, J = 0.9 Hz, 1H),
1
3
1
3
6
5
7
(
2
.86–6.91 (m, 2H), 7.28–7.32 (m, 2H) ppm; C NMR: d = 22.4, 48.2,
5.3, 71.1, 113.8 (2”C), 113.9, 127.0, 136.2, 142.5, 159.0 ppm; MS (EI,
0 eV): m/z (relative intensity): 192 (1), 174 (2), 159 (4), 137 (100), 135
1
2
(
(
5
100), 51 (13), 40 (46); elemental analysis calcd (%) for C13
265.26): C 58.86, H 5.70, N 5.28, O 30.16; found: C 58.26, H 5.82, N
.26.
H15NO
5
3
11), 109 (28), 94 (17), 77 (17); MS (CI, NH ): m/z (relative intensity):
10 (2), 192 (6), 175 (100), 154 (9), 137 (9).
[
58]
3
-Methyl-1-(2-tosylaminophenyl)-but-3-en-1-ol 13b:
was obtained from 2-tosylamino-benzaldehyde (1.0 mmol)and polymer
b as a white solid (295 mg, 89%)after purification by flash chromatog-
= 0.45); H NMR: d = 1.69
s, 3H), 2.19 (dd, J = 4.2, 13.8 Hz, 1H), 2.28 (dd, J = 9.9, 13.8 Hz, 1H),
.37 (s, 3H), 2.56 (brs, 1H), 4.68 (dd, J = 9.9, 4.2 Hz, 1H), 4.75 (s, 1H),
.92 (s, 1H), 7.04 (m, 2H), 7.18–7.24 (m, 3H), 7.49 (d, J = 8.1 Hz, 1H),
.70 (d, J = 8.1 Hz, 2H), 8.57 (s, 1H) ppm; C NMR: d = 21.4, 22.0,
5.1, 71.3, 114.6, 121.7, 124.4, 127.0, 127.5, 128.4, 129.5, 132.0, 135.8,
36.9, 141.3, 143.6 ppm; MS (EI 70 eV): m/z (relative intensity): 331 (4),
Compound 13b
Ethyl 4-hydroxy-4-(4-methoxyphenyl)-2-methylenebutanoate (12c): Com-
pound 12c was obtained from 4-methoxy-benzaldehyde (0.5 mmol)and
polymer 1c as a colorless oil (90 mg, 72%)after purification by flash
1
1
raphy (petroleum ether/ethyl acetate 8:2, R
(
f
chromatography (petroleum ether/ethyl acetate 8:2,
H NMR: d = 1.31 (t, J = 7.2 Hz, 3H), 2.66 (ddd, J = 14.1, 7.8, 0.6 Hz,
R
f
=
0.22);
1
2
4
7
4
1
2
1
H), 2.67 (d, J = 3.9 Hz, 1H), 2.76 (ddd, J = 14.1, 4.5, 0.9 Hz, 1H), 3.80
1
3
(s, 3H), 4.22 (q, J = 7.2 Hz, 2H), 4.84 (ddd, J = 7.8, 4.5, 3.9 Hz, 1H),
5
7
7
.58 (ddd, J = 1.2, 0.9, 0.6 Hz, 1H), 6.23 (d, J = 1.2 Hz, 1H), 6.87 and
.28 (AA’BB’ system, 4H)ppm; C NMR: d = 14.1, 42.4, 55.2, 61.0,
2.7, 113.7 (2”C), 126.9 (2”C), 128.0, 136.1, 137.2, 158.9, 167.7 ppm; MS
1
3
75 (5), 158 (100), 143 (30), 120 (41), 91 (36), 65 (18) ppm; IR (KBr): n˜
À1
(EI, 70 eV): m/z (relative intensity): 250 (2), 204 (5), 137 (100), 109 (20),
4 (11), 77 (12), 57 (31), 31 (33); elemental analysis calcd (%) for
(250.29): C 67.18, H 7.25, O 25.57; found: C 66.97, H 7.35.
=
3491, 3239, 2922, 1159 cm
.
9
General procedure for the InX
Aldehyde (1.0 mmol)and InBr
pension of polymer (1.0 g, 1.4 mmol)in CH
was stirred at 258C for 3 h and was then quenched with HCl (0.1m,
0 mL). The polymer was filtered and was washed first with diethyl ether
6”30 mL)and then with THF (6”30 mL .) The filtrate was extracted
with diethyl ether, washed with brine (50 mL), dried over MgSO , and
3
-promoted allylstannation of aldehydes:
or InCl (1.0 mmol)were added to a sus-
Cl . The reaction mixture
14 18 5
C H O
3
3
4
1
-Hydroxy-2-methylene-4-(4-nitrophenyl)butanenitrile (11d): Compound
1d was obtained from 4-nitrobenzaldehyde (0.5 mmol)and polymer 1d
2
2
as a yellow solid (80 mg, 73%)after purification by flash chromatogra-
1
(
1
phy (petroleum ether/ethyl acetate 8:2, R
f
= 0.10); H NMR: d = 2.40
(
d, J = 3.0 Hz, 1H), 2.65–2.67 (m, 2H), 5.09–5.14 (m, 1H), 5.80 (s, 1H),
4
1
3
6
4
1
1
.00 (s, 1H), 7.56 and 8.23 (AA’BB’ system, 4H)ppm; C NMR: d =
4.2, 71.1, 118.2, 118.8, 124.0 (2”C), 126.6 (2”C), 134.1, 147.7,
49.6 ppm; MS (EI, 70 eV): m/z (relative intensity): 170 (70), 169 (100),
concentrated under vacuum. The crude product was purified by chroma-
tography on silica gel. The resulting polymer 5c (obtained with use of
InBr as a promoter), on the other hand, was washed with absolute etha-
3
nol (4”40 mL)and dried under vacuum (0.5 mbar)at 60 8C for 5 h to be
reused. Polymer 5c was obtained as a white resin and was found to be a
52 (18), 142 (11); MS (CI, NH
3
): m/z (relative intensity): 236 (100), 219
(218.21): C
(
45), 171 (8); elemental analysis calcd (%) for C11
H
10
N
2
O
3
À1
119
60.55, H 4.62, N 12.84, O 22.00; found: C 60.30, H 4.95, N 12.48.
SnÀBr-type polymer containing 1.22 mmol of SnÀBrg
.
Sn MAS-
NMR: d = +133 ppm; elemental analysis (%)found: C 66.72, H 6.85,
Sn 14.43, Br 11.82.
[
59]
Ethyl 4-hydroxy-2-methylene-4-phenylbutanoate (9c):
Compound 9c
was obtained from benzaldehyde (0.5 mmol)and polymer 1c as a color-
Acknowledgements
less oil (100 mg, 91%)after purification by flash chromatography (petro-
1
leum ether/ethyl acetate 88:12, R
f
= 0.10); H NMR: d = 1.32 (t, J =
We gratefully acknowledge “Nantes MØtropole” for a grant (J.-M.C.)as
well as the CNRS and the University of Nantes for financial support. We
are indebted to Dr. Gilles Montavon and ValØrie BossØ from Subatech,
UMR CNRS 6457, Ecole des Mines de Nantes, for carrying out ICP-MS
analyses, and Dr. Alain Barreau from Institut des MatØriaux Jean
Rouxel, UMR CNRS 6502, for EDS measurements. We also wish to ex-
press our gratitude to Crompton GmbH for the gift of organotin starting
materials and to the referees of this paper, whose pertinent remarks have
allowed a considerable improvement of the manuscript.
7
1
8
7
.2 Hz, 3H), 2.66 (dd, J = 14.1, 8.4 Hz, 1H), 2.78 (dd, J = 14.1, 4.2 Hz,
H), 2.92 (d, J = 3.6 Hz, 1H), 4.20 (q, J = 7.2 Hz, 2H), 4.87 (ddd, J =
.4, 4.2, 3.6 Hz, 1H), 5.58 (d, J = 1.2 Hz, 1H), 6.22 (d, J = 1.2 Hz, 1H),
1
3
.23–7.37 (m, 5H)ppm; C NMR: d = 14.2, 42.6, 61.1, 73.2, 125.7 (2”
C), 127.5, 128.2, 128.4 (2”C), 137.2, 144.0, 167.8 ppm; IR (KBr): n˜ =
3
7
1
7
460, 3074, 3030, 2981, 2960, 2929, 2872, 1715, 1630, 1500, 1455, 1193,
56, 700 cm ; MS (EI, 70 eV): m/z (relative intensity): 220 (2), 175 (5),
74 (18), 157 (7), 129 (15), 114 (88), 107 (100), 105 (18), 86 (73), 79 (71),
7 (46), 69 (21), 68 (48), 40 (20), 29 (14).
À1
Ethyl 4-(4-bromophenyl)-4-hydroxy-2-methylenebutanoate (10c): Com-
pound 10c was obtained from 4-bromo-benzaldehyde (0.5 mmol)and
polymer 1c as a colorless oil (144 mg, 96%)after purification by flash
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R
f
=
0.31);
1
H NMR: d = 1.30 (t, J = 7.2 Hz, 3H), 2.60 (dd, J = 14.1, 8 Hz, 1H),
6826
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Chem. Eur. J. 2006, 12, 6816 – 6828

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[
[
1
19
39] The broadness of the Sn resonances associated with the organotin
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5,37
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127
119
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Sn–X dipolar interac-
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3
14
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Received: December 20, 2005
Published online: June 6, 2006
6828
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Chem. Eur. J. 2006, 12, 6816 – 6828