Preparation of α-substituted γ-alkoxyallylstannanes from β-tributylstannyl acrolein acetals: Scope of the method and primary rationalization of the obtained results

Article abstract of DOI:10.1016/j.jorganchem.2004.10.022

α-Substituted γ-alkoxyallylstannanes were obtained from β-tributylstannyl acrolein acetals when reacted with lower order magnesium cyanocuprates in the presence of boron trifluoride at low temperature. In the case of n-alkylcyanocuprates an anti S_N2′ substitution on a cisoid conformation appears to be the main reaction pathway. However, subtle competitions with other mechanisms may occur depending on the experimental conditions, on the reagents or on the substrates. These drawbacks constitute limitations for the use of the method especially when enantioenriched α-substituted γ-alkoxyallylstannanes are desired.

Full text of DOI:10.1016/j.jorganchem.2004.10.022

Journal of Organometallic Chemistry 690 (2005) 659–673
www.elsevier.com/locate/jorganchem
Preparation of a-substituted c-alkoxyallylstannanes from
b-tributylstannyl acrolein acetals: scope of the method and
primary rationalization of the obtained results
*
Florian Fliegel, Isabelle Beaudet , Sandrine Watrelot-Bourdeau,
*
Nicolas Cornet, Jean-Paul Quintard
` ´
Laboratoire de Synthese Organique, UMR CNRS 6513 and FR CNRS 2465, Faculte des Sciences et des Techniques de Nantes,
`
2 Rue de la Houssiniere, BP 92208, 44322 Nantes Cedex 3, France
Received 20 July 2004; accepted 11 October 2004
Available online 18 November 2004
Abstract
a-Substituted c-alkoxyallylstannanes were obtained from b-tributylstannyl acrolein acetals when reacted with lower order mag-
nesium cyanocuprates in the presence of boron trifluoride at low temperature. In the case of n-alkylcyanocuprates an anti SN20 sub-
stitution on a cisoid conformation appears to be the main reaction pathway. However, subtle competitions with other mechanisms
may occur depending on the experimental conditions, on the reagents or on the substrates. These drawbacks constitute limitations
for the use of the method especially when enantioenriched a-substituted c-alkoxyallylstannanes are desired.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Vinyltins; Allyltins; b-Tributylstannyl acrolein acetals; a-Substituted c-Alkoxyallylstannanes; Copper cyanocuprates; SN20 substitution
1. Introduction
reactions of aldehydes involving enantiopure chiral
c-oxygenated allylstannanes or chiral aldehydes [8,9].
In order to obtain achiral c-alkoxyallylstannanes sev-
eral methods have been employed. Hydrostannation of
alkoxyallenes under free radical conditions or under pal-
ladium catalysis usually affords a mixture of isomers
[10–12] while metallation of allyl acetals [13] or allyl
ethers [14,15] followed by quenching with a triorganotin
halide works nicely with a strong preference for the Z-
isomer in the last case due to the chelation of the metal
with oxygen.
When c-oxygenated allylstannanes with the E config-
uration were desired, the best stereochemical control
was obtained through stannylcupration of a,b-enals
with higher order stannyl cyanocuprates and further
quenching with alkoxymethyl chloride or triorganosilyl-
chloride [16,17]. In this last case, the obtaining of (Z)-c-
siloxyallylstannanes was achieved through reaction
of trialkylstannylllithium on a,b-enals followed by
Due to their efficiency in the stereoselective synthesis
of polyhydroxylated targets upon reaction with a- or b-
oxygenated aldehydes [1,2] or iminium salts [3–5], (c-
alkoxy)- and (c-silyloxy)allylstannanes have become
useful reagents for organic chemists. This interest has
been amplified by the fact that an a-substituent or a
change in the geometry of the double bond could some-
times modify in a major way the stereochemical course
of the allylstannation reaction [6,7]. Furthermore stereo-
convergent effects have been observed in allylstannation
*
Corresponding authors. Tel.: +33 2 51 12 54 09; fax: +33 2 51 12
54 02 (I. Beaudet), Fax: +33 2 51 12 54 02 (J.-P. Quintard).
E-mail addresses: beaudet@chimie.univ-nantes.fr (I. Beaudet),
quintard@chimie.univ-nantes.fr (J.-P. Quintard).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.10.022

660
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
quenching with triorganosilyl triflates [16]. Further-
more, the use of readily available b-tributylstannylacro-
lein (treatment of the acetal on wet silica gel) [18–20] has
also been proved to provide a selective access to a-
substituted c-siloxyallyltributylstannanes [5,17].
boron trifluoride. The easy access to pure (E)- or (Z)-
b-tributylstannylacrolein acetals using appropriate
experimental conditions [37,38] might open interesting
possibilities and help in a comprehensive study allowing
an evaluation of the effective potential of this strategy.
The synthesis of enantioenriched c-alkoxyallylstann-
anes can be achieved from allyl ethers derived from
enantioenriched chiral alcohols using a metallation/
tributyltin halide trapping sequence [21,22] or via tran-
salkoxylation of a c-methoxyallylstannane with a chiral
alcohol [23]. However, these methods have been
strongly challenged by the stereospecific boron trifluo-
ride promoted rearrangement of enantioenriched
(E)-a-alkoxyallylstannanes into enantioenriched (Z)-
c-alkoxyallylstannanes [24]. Accordingly, the synthesis
of a-alkoxyallylstannanes previously described in achi-
ral series [25–27] became of crucial interest when enan-
tioenriched chiral a-oxygenated species were involved.
The pioneering preparation based on separation of dia-
stereomeric mixtures of a-(menthyloxymethyl)crotyl-
tributylstannanes [28,29] has been rapidly replaced by
enantioselective preparations.
The first one was the enantioselective reduction (BI-
NAL-H) of a,b-ethylenic acylstannanes which afforded
enantioenriched a-stannylalcohols subsequently trapped
as methoxymethyl ethers [30,31]. The second one was
the selective deprotonation of carbamates derived from
allylic alcohols followed by trapping with a triorganotin
halide. This last method developed mainly by Hoppe
was first applied to carbamates of enantiopure allylic
alcohols using sec-butyllithium-TMEDA for deprotona-
tion and subsequently extended to the asymmetric
deprotonation of racemic crotylcarbamates and related
species using n-butyllithium/(ꢀ)-sparteine [32–34].
Using appropriate experimental conditions (direct trap-
ping of the lithiocrotyl carbamate by triorganotin halide
or trapping after transmetallation with titanium tetrai-
sopropoxide), the (Z)-c-oxygenated a-substituted all-
ylstannanes can be obtained selectively with the R or
with the S configuration at the a-carbon centre related
to tin [34].
2. Results
In order to obtain efficiently c-alkoxyallylstannanes
from b-tributylstannyl acrolein acetals, the reaction
must be driven to a clean SN20 reaction as observed with
non stannylated allylic acetals when reacted with aryl or
vinyl copper reagents in the presence of boron trifluoride
[39–41].
In the present case the difficulties might arise from the
easy transmetallation of Sn–C bond by organolithium
reagents [42] and by higher order cyanocuprates
[43,44] or from a competitive SN2 pathway [41].
Accordingly, preliminary experiments have been
achieved using different types of methyl copper reagents
in the presence of boron trifluoride (Scheme 1).
The obtained results, discussed in our early report
[35], have allowed the following observations:
ꢁ with Me2CuLi, the SN20 pathway was shown to be the
major one but substitution products were obtained as
a mixture of 2E and 2Z isomers and an important
contamination by 3 and 4 was observed;
ꢁ with MeCu Æ LiBr in the presence of Me2S the trans-
metallation reaction only was observed;
ꢁ with MeCu Æ LiX or MeCuCNLi the SN20 reaction
was the major or exclusive pathway with a high pref-
erence for the Z-isomer.
On the basis of these results, it was deduced that the
use of organocopper reagents or lower order cyanocup-
rate reagents in ether seems preferable to obtain the
higher yields in 2 (SN20 product). Furthermore, since
Grignard reagents have a lower propensity to transmet-
allate the vinylic tin–carbon bond, we chose to use
mainly lower order magnesium cyanocuprates to
achieve this transformation with different R groups.
The obtained results reported in Table 1 demonstrate
an efficient preparation of a-substituted c-ethoxyallylst-
annanes with isolated yields in the range 60–95% and a
high preference for the Z-isomer (80–100%). Further-
In this context, in spite of the efficiency of these meth-
ods, we decided to investigate thoroughly our initial
reports about synthesis of a-substituted c-alkoxyallylst-
annanes [35] or a-substituted c-aminoallylstannanes [36]
by reacting (E)-b-tributylstannylacrolein acetals or amino
acetals with organocopper reagents in the presence of
OR1
OR1
RM / L.A.
solvent
R
Bu3Sn
Bu3Sn
R
+
OR1
+
RSnBu3
OR1
Bu3Sn
-78˚C, 3h
1aE (R1 = Et)
1bE (R1 = Bn)
1cE [(OR1)2 = O-(CH2)3-O]
2 (SN2')
3 (SN2)
4
(transmetallation)
Scheme 1.

F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
661
Table 1
Synthesis of c-alkoxyallylstannanes from vinyltin acetals 1a–c
Entry
1
Substrate
Organocopper reagenta
c-Alkoxystannane
No.
Yield (Z/E)b
1aE
MeCu(CN)Li
2a
81 (80/20)
Me
Bu3Sn
Et
OEt
OEt
2
3
1aE
1aE
1aE
1aE
1aE
1aE
1bE
1bE
1aZ
1aZ
1aZ
1cE
1cE
1cZ
1cZ
EtCu(CN)MgBr
2b
2c
2d
2e
2f
75 (94/6)
Bu3Sn
n-Bu
n-BuCu(CN)MgBr
i-PrCu(CN)MgCl
t-BuCu(CN)MgCl
Me3SiCH2Cu(CN)MgCl
PhMe2SiCH2Cu(CN)MgCl
MeCu(CN)MgCl
t-BuCu(CN)MgCl
EtCu(CN)MgBr
68 (96/4)
Bu3Sn
i-Pr
OEt
4
85 (98/2)
Bu3Sn
t-Bu
OEt
OEt
5
70 (98/2)
Bu3Sn
Me3SiCH2
6
95 (100/0)
58 (100/0)
51 (100/0)
87 (100/0)
80 (100/0)c,d
85 (100/0)c,d
97 (100/0)c
53 (50/50)
68 (55/45)
68 (100/0)c,d
52 (100/0)c,d
Bu3Sn
PhMe2SiCH2
Bu3Sn
OEt
7
2g
2h
2i
OEt
Me
8
Bu3Sn
OBn
OBn
OEt
OEt
t-Bu
9
Bu3Sn
Et
10
11
12
13
14
15
2b
2d
2e
2j
Bu3Sn
i-Pr
i-PrCu(CN)MgCl
t-BuCu(CN)MgCl
EtCu(CN)MgBr
Bu3Sn
t-Bu
Bu3Sn
Et
OEt
O
Bu3Sn
i-Pr
(CH2)3-OH
(CH2)3-OH
(CH2)3-OH
(CH2)3-OH
i-PrCu(CN)MgCl
i-PrCu(CN)MgCl
t-BuCu(CN)MgCl
2k
2k
2l
Bu3Sn
i-Pr
O
O
O
Bu3Sn
t-Bu
16
Bu3Sn
a
Reactions were performed in ether at ꢀ78 to ꢀ30 ꢁC using 3 equiv. of organocopper reagent and 3 equiv. of boron trifluoride etherate.
Isolated yields in SN20 substitution products after liquid chromatography on deactivated alumina.
Conversion rate (NMR evaluation).
b
c
d
The SN2 compound was also observed (5% for entries 10–11, 10% for entry 15 and 15% for entry 16).

662
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
more, as expected, this reaction can easily be extended to
the preparation of a-substituted c-benzyloxyallylstann-
anes, 2h and 2i (Table 1, entries 8,9), which have a higher
potential interest for organic synthesis due to the
possible hydrogenolysis of the benzylic ether function
[9].
the SN2 products 3k and 3l (respectively, 10% and
15%) was observed (entries 15,16).
The last parameter (a-vinylic substituent related to
tin on the substrate) was examined through consider-
ation of b-tributylstannyl crotonaldehyde diethyl acetal
1dE which was reacted with (trimethylsilyl)methyl mag-
nesium cyanocuprate according to Scheme 2. Subse-
quent modulations of the experimental conditions are
reported in Table 2.
When compared to reactions involving b-tributyl-
stannylacrolein acetals, the presence of the methyl group
in 1dE strongly modifies the distribution between SN2
and SN20 products. When reagents were used in a ratio
close to stoechiometry or when solution S2 was added
on S1 at ꢀ80 ꢁC, the SN2 product 3m appeared to be
the major component. However when we increased the
amount of boron trifluoride (compared to the amount
of RCu(CN)MgCl as obtained for addition of S1 into
S2), the SN20 product became the major component.
Furthermore, use of a higher reaction temperature
(ꢀ40 ꢁC) appeared to be more favourable to SN20
reaction. Finally, while (Z)-allylstannane (2mZ) was ob-
tained as the major component when the reactions were
At this stage, a comprehensive study of the reaction
requires the evaluation of structural effects such as
geometry of the double bond in 1, influence of a cyclic
acetal having a higher propensity for chelation with bor-
on trifluoride or influence of a substituent on the vinylic
carbon bearing the stannyl group. The results on the
first two points are reported in Table 1 (comparison of
entries 2–5 with entries 10–16). Starting from 1aZ, the
SN20 products 2b, 2d and 2e were obtained as pure Z-
isomers (in the limit of the NMR detection) with a small
contamination (5%) by SN2 products 3b and 3d. When
the cyclic acetal 1cE was used as starting material (en-
tries 13,14), once more the SN20 substitution products
2j and 2k were obtained but as a mixture of E- and Z-
isomers. The weakness of the diastereoselectivity can
be solved starting from 1cZ (2k and 2l were obtained
as pure Z-isomers) but another contamination due to
R
Bu3Sn
Me
Bu3Sn
Me
RCu(CN)MgCl
Bu3Sn
OEt
Me OEt
+
+
Me
Bu3Sn
OEt
BF3.OEt2, ether
O
OEt
H
R
R = CH2SiMe3
1dE
2m
Scheme 2.
3m
5
Table 2
Reaction of Me3SiCH2Cu(CN)MgCl with (E)-Bu3Sn–C(Me)@CH–CH(OEt)2
Entry
Experimental conditionsa
Products distributionb
SN20 products
SN2 product
Aldehydec
2mZ
2mE
3m
74
5
1
2
3
(1) CuCN (1.2eq) + RMgCl (1.2eq), ꢀ40 ꢁC, 15 min then ꢀ80 ꢁC
(2) Addition of BF3 Æ OEt2 (1.2eq) then 1dE (1eq), ꢀ80 ꢁC, 1 h
3
23
0
(1) CuCN (1.5eq) + RMgCl (1.5eq), ꢀ50 ꢁC, 2 min then ꢀ80 ꢁC
11
3
37
32
52
59
0
6
(2) Addition of 1dE (1eq) + BF3 Æ OEt2 (1.5eq), ꢀ80 ꢁC, 2 h
S1 = CuCN (2eq) + RMgCl (2eq), ꢀ45 ꢁC, 30 min
S2 = 1dE (1eq) + BF3 Æ OEt2 (3eq), ꢀ80 ꢁC, 10 min
(S2 cannulated on S1 at ꢀ80 ꢁC, 1 h)
4
S1 = CuCN (1.5eq) + RMgCl (1.5eq), ꢀ40 ꢁC, 10 min
S2 = 1dE (1eq) + BF3 Æ OEt2 (3eq), ꢀ40 ꢁC, 10 min
(S1 at ꢀ80 ꢁC cannulated on S2 at ꢀ80 ꢁC, 1 h)
S1 = CuCN (2eq) + RMgCl (2eq), ꢀ45 ꢁC, 40 min
S2 = 1dE (1eq) + BF3 Æ OEt2 (3eq), ꢀ45 ꢁC, 40 min
(S2 at ꢀ40 ꢁC cannulated in S1 at ꢀ40 ꢁC, 1 h)
59
36
29
31
12
12
0
5
21
a
In this set of experiments R is Me3SiCH2 and reactions were performed in ether. Stoechiometry and reaction temperature are mentioned in the
table. For entries 3–6 the cyanocuprate solution (S1) and the 1dE/ BF3 Æ OEt2 solution (S2) were prepared separately and one of these two solutions
was cannulated on the other at low temperature before being allowed to react at this temperature during the indicated time.
b
NMR evaluation on the crude mixture.
c
Upon treatment of 1dE with BF3 Æ OEt2 and subsequent hydrolysis (without reaction with RCu(CN)MgCl), aldehyde 5 was obtained in a ratio
E/Z = 84/16 accompanied with a small amount of isomerized vinylstannane 1dZ which seems to be less easily hydrolysed than its E-isomer.

F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
663
n-Bu
Bu3Sn
O
Me
Bu3Sn
+
*
n-BuCu(CN)MgCl
n
O
OH
n
Bu3Sn
O
OH
O
BF3.OEt2(3eq), ether
-78˚C to -40˚C
n
n-Bu
Me Me
Me Me
Me
1eE
1fE
2n (E+Z) , 82% yield
2p (E+Z) , 88% yield
(n=0)
(n=1)
3p
6p (see scheme 5)
Scheme 3.
performed with a large excess of boron trifluoride ether-
ate, the preference turned to the E-isomer when the SN2
is the main one for reactions performed with lower rates
of Lewis acid at ꢀ80 ꢁC.
The lower Z/E selectivity observed with 1eE might be
due to a higher flexibility of the five-membered ring ace-
tals or to different chelation pathways when compared
to their six-membered analogues.
Finally, it is worth noticing that secondary a,c- or
a,a0-disubstituted products have been isolated. Their
formation is the result of a subsequent SN2 or SN20 at-
tack onto an initially formed SN2 substitution product
(Scheme 5).
Obviously these last results demonstrate a subtle
competition between SN20 and SN2 pathways when
1dE was involved, possibly slightly complicated by com-
petitive addition on aldehyde 5 (cf. Table 2, footnote c).
Due to these problems, we decided to focus our efforts
on the rationalization of the SN20 substitution of b-tribu-
tylstannylacrolein acetals derived from (2R,3R)-butane-
diol (1eE) or from (2R,4R)-pentanediol (1fE and 1fZ)
by using the stereochemical information to improve the
understanding of the reaction. In the case of n-BuCu-
CNMgCl, the reaction occurs as depicted in Scheme 3
and the results are summarized in Table 3 (entries 1,4).
From these data, it appears clearly that (2R,4R)-pen-
tanediol acetal 1fE allows improved Z selectivity in
obtaining SN20 products when compared to (2R,3R)-
butanediol acetal 1eE and that configuration of the
starting vinyltin acetal is of crucial importance since
1fZ appears to be unreactive (Table 3, entry 10).
While use of higher order lithium methyl cyanocup-
rates (Table 3, entries 2,3) led to poor selectivities (both
SN2 and SN20 products were obtained and SN20 products
were obtained as mixtures of E and Z isomers), lower
order magnesium cyanocuprates afforded SN20 adducts
with a high Z selectivity (Z/E = 79/21–94/6) but with a
stereocontrol on the new created centre which was
strongly modified by the size of the entering group
(Table 3, entries 4,6–9), as illustrated by the observed
diastereomeric excesses which decrease according to
the following sequence n-Bu (88%) > Me3SiCH2
(76%) > i-Pr (68%) > t-Bu (40%) in the RCu(CN)MgCl
series. This type of selectivity seems to be higher for
the obtained E-isomers but unexploitable for prepara-
tive purpose due to the low yield in this isomer.
According to this scheme, a mixture of 6o and 7o was
obtained in 20% yield for R = Me (entry 3) while a 3%
yield of 6p was obtained for R = n-Bu (entry 4).
3. Discussion
The above results demonstrate the possible access to
a-substituted c-alkoxyallylstannanes from b-tributyl-
stannyl acrolein acetals upon reaction with cyanocup-
rates in the presence of boron trifluoride.
The higher Z selectivities in c-alkoxyallylstannanes
(SN20 substitution products) were obtained using lower
order magnesium cyanocuprates with diethyl or diben-
zyl b-tributylstannyl acrolein acetals and an increased
Z selectivity was observed for (Z)-b-tributylstannyl
acrolein acetals with a concomitant lower reactivity
(Z-acetals derived from (2R,4R)-pentanediol appear to
be unreactive).
In the reactions leading to the higher Z selectivity
(use of n-BuCu(CN)MgCl) the creation of the new
asymmetric centre with an S configuration can be ex-
plained by an anti SN20 reaction on a cisoid conforma-
tion according to Scheme 6.
Such an explanation has already been used to rational-
ize this type of substitution on purely organic allylic ace-
tals [41] but the obtained results require some comments.
The absolute configuration of the newly created cen-
tre has been assigned as (S) for 2pZ (SN20 substitution
by n-butyl group) on the basis of its [a]D value of
+117.5 taking into account the [a]D value of ꢀ3.2 ob-
tained for compound 2q and the [a]D values around
+120 reported by Marshall [24] for the (S)-enantiomer
of (c-alkoxyallyl)stannanes having very similar struc-
tures (Scheme 4). This assignment has been discussed
in a previous report [35].
(1) This SN20 reaction seems to be highly sensitive to
steric effects, both for the approach of the Lewis
acid and the nucleophiles. While approach of the
Lewis acid on the less hindered oxygen seems able
to drive efficiently the stereoselectivity when pri-
mary alkyl cyanocuprates are involved, the steric
interaction between the equatorial methyl group
on the acetal and the entering nucleophile can

664
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
Table 3
Reaction of cyanocuprates with chiral b-tributylstannyl acrolein acetals
Entry
Substrate
Organocopper reagenta
Obtained product
No.
Distribution productsb
Yieldsd
2(SN20)
3(SN2)
Z (de)
E (de)
Me
OH
1
1eE
n-BuCu(CN)MgCl
2n
57 (nd)
43 (nd)
–
82
Bu3Sn
n-Bu
O
Me
2
3
1fE
1fE
Me2Cu(CN)Li2
2o
3o
19 (nd)
18 (64)
61c
20
35
37
48
Bu3Sn
Bu3Sn
O
OH
Me Me
Me
O
OH
Me2Cu(CN)Li2,LiBr
47c
Me Me Me
Bu3Sn
n-Bu
O
OH
4
5
6
7
8
9
1fE
1fE
1fE
1fE
1fE
1fE
1fZ
n-BuCu(CN)MgCl
Bu2Cu(CN)Li2
2p
2q
2r
2r
2s
2t
–
93 (88)
7 (nd)
–
–
–
–
–
–
82
17e
65
64
80
78
0
Me Me
[α]D = + 117.5
Bu3Sn
Bu3Sn
O
OH
100e
–
Me Me
[α]D = - 3.2
O
OH
i-PrCu(CN)MgCl
i-Pr2Cu(CN)(MgCl)2
t-BuCu(CN)MgCl
Me3SiCH2Cu(CN)MgCl
94 (68)
93 (46)
79 (40)
91 (76)
–
6c
i-Pr
Me Me
Bu3Sn
i-Pr
O
O
OH
Me Me
7 (nd)
21c
9c
Bu3Sn
t-Bu
OH
Me Me
Bu3Sn
Me3Si
O
OH
Me Me
10
RCu(CN)MgCl;
R = Et, n-Bu, i-Pr, t-Bu
No reaction
–
a
Reactions were performed in the presence of BF3 Æ OEt2 (3 equiv.) in ether from ꢀ78 to ꢀ40 ꢁC.
nd: not determined.
b
c
For these E-allylstannanes, a single diastereomer was obtained in the limits of NMR detection.
Overall yields of substitution products (SN2 + SN20).
SN20 reduction product (hydrogen transfer).
d
e
challenge the accessibility of the Lewis acid to the
less hindered oxygen, giving a lower anti SN20/syn
SN20 ratio.
Such an explanation might account for the decrease
of diastereomeric excess in the obtained a-substituted
c-alkoxyallylstannanes when moving from n-Bu

F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
665
S
S
n-Bu
S
n-Bu
n-Bu
Bu3Sn
O
O
Bu3Sn
Bu3Sn
O
O
O
OH
Me Me
Me
Ph
α
α
α
D = + 117.5 (88% de)
D = + 119 (95% ee)
Marshall [24]
D = + 116 (95% ee)
Marshall [24]
2pZ
Scheme 4.
SN2'
Bu3Sn
Bu3Sn
O
OH
Me Me
3o (R = Me)
Bu3Sn
+
R
or SN2
R
R
R
R
6o (R = Me)
7o (R = Me)
3p (R = n-Bu, not observed)
6p (R = n-Bu)
Scheme 5.
Bu3Sn
n-Bu
H
H
BF3
Bu3Sn
Bu
anti SN2'
S
O
R
R
O
OH
O
Me
H
Me
Me Me
H
1fE
2pZ
Scheme 6.
Cu(CN)MgCl to Me3SiCH2Cu(CN)MgCl, i-PrCu-
(CN)MgCl and t-BuCu(CN)MgCl. A similar trend
has been already observed in substitution of allylic
mesylates [45].
4. Conclusion
The preparation of (Z)-a-substituted c-alkoxyallylst-
annanes has been shown to be possible by reacting mag-
nesium cyanocuprates with b-tributylstannylacrolein
acetals in the presence of boron trifluoride etherate at
ꢀ78 to ꢀ40 ꢁC in ether. With less hindered systems,
an anti SN20 substitution on a cisoid conformation seems
to be the main reaction pathway, but subtle competi-
tions are likely to occur, depending on the nature of
the counterion on the cyanocuprate, on the size of the
entering nucleophile or on the temperature.
(2) The fact that higher Z selectivities were obtained
using magnesium cyanocuprates instead of lithium
cyanocuprates might be due to the bidentate char-
acter of magnesium (which might interact both with
the organocopper moiety and with the syn oxygen
of the acetal).
(3) In any case, the anti SN20 pathway on the cisoid
conformation cannot fully explain the obtained
results. Other mechanisms are obviously involved,
as for instance a syn SN20 substitution on a cisoid
conformation, an anti SN20 substitution on a tran-
soid conformation (stereoselective obtaining of 2E
derivatives), or an SN1 mechanism when a higher
stabilisation of an intermediate cation can be con-
sidered, as for instance in the case of b-tributylstan-
nyl crotonaldehyde acetals. The interference of
oxonium intermediates has already been proposed
in the case of substitution of deuterium-labelled sat-
urated acetals [46].
5. Experimental
5.1. General
1H, 13C and 119Sn spectra were recorded on Bruker AC
200 or Bruker ARX 400 spectrometers. Chemical shifts
are given in ppm as d values related to tetramethylsilane
(1H, 13C) or tetramethylstannane (119Sn) and coupling
constants are given in Hz (CDCl3 was used as solvent at
300 K when nothing else is mentioned). Mass spectra
were obtained in direct introduction mode or in
GC/MS mode using a Hewlett–Packard Engine 5989A
apparatus in EI (70 eV) or CI (using NH3 as reacting
gas) mode. Organostannyl fragments are given for 120Sn
(4) Due to the use of a large excess of boron trifluoride
and cyanocuprate (3 equiv.) and to the influence of
temperature on the effective structure of the
reagents, too many parameters remain unknown
to allow further reasonable discussion.

666
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
which means that the given abundance are broadly one
third of the overall abundance of the organostannyl frag-
ment when compared to organic ones. When high resolu-
tion spectra were done, they were recorded on a Jeol
SX102 apparatus in FAB+ mode (10 kV), using glycerol
matrix. IR spectra (film in NaCl windows) were recorded
with a Perkin–Elmer 1420 or a Bruker IFS Vector 22
apparatus. Optical rotations were measured using an
‘‘Optical Activity AA10’’ apparatus or a Perkin–Elmer
341 apparatus. Elemental analyses were performed by
CNRS microanalysis centre (Vernaison). Liquid chroma-
tography separations were achieved on silicagel Si 60 (40–
63 or 63–200 lm) or on activated alumina (50–200 lm)
and TLC analyses on silica-coated plates (Merck Kiesel-
gel 60F254). The solvents used in the reactions are freshly
distilled ones, dried on sodium–benzophenone (diethyle-
ther and THF) or on calcium hydride. When reactions
were performed in Schlenk tubes, the reactor (eventually
containing solid salts like CuCN) was first dried by flame
heating under vacuum and placed under inert atmosphere
(argon). The other reagents were added by syringue meth-
od in their solvent.
5.2.1.2. 2-Ethynyl-1,3-dioxane (5.2 g, 60% yield). 1H
4
NMR: d = 1.50–1.90 (m, 2H), 2.58 (d, 1H, J1H = 1.8),
4
3.76 (m, 2H), 4.12 (m, 2H), 5.31 (d, 1H, J1H = 1.8);
13C NMR (CDCl3, 300K): d = 25.5, 64.5 (2C), 73.8,
78.2, 89.6; IR: m = 3293, 2961, 2907, 2858, 2133, 1414,
1105, 1022, 872, 795 cmꢀ1; MS: m/z (%) = 112 (MÅ+,
10), 111 (75), 81 (40), 55 (100), 53 (100).
5.2.1.3. (4R,6R)-2-Ethynyl-4 6-dimethyl-1 3-dioxane
(mp = 89 ꢁC, white crystals, 8.9 g, 82% yield). 1H
3
NMR: d = 1.26 (d, 3H, J1H = 6.4), 1.30–1.45 (m, 1H),
1.39 (d, 3H, J1H = 8.5), 1.91 (ddd, 1H, J1H = 13.2,
3
2
3
4
3J1H = 11.0, J1H = 6.0), 2.52 (d, 1H, J1H = 1.6), 4.03
3
(qdd, 1H, J1H = 11.0, J3H = 6.4, J1H = 2.7), 4.37
3
3
3
(qdd, 1H, J1H = 6.0, J3H = 8.5, J1H = 2.2), 5.57 (d,
3
3
1H, J1H = 1.6); 13C NMR: d = 17.0, 21.6, 36.5, 68.3,
4
68.5, 72.4, 79.6, 84.5; IR: m = 3249, 2975, 2937, 2890,
2130, 1384, 1149, 1101, 991, 708 cmꢀ1; MS: m/z
(%) = 139 (MÅ+–H, 29), 125 (9), 99 (19), 81 (21), 71
(38), 55 (72), 45 (49), 42 (100); [a]D = +16.8 (c = 1.016
in CHCl3).
5.2. Organic starting materials
5.2.2. Preparation of 1,1-diethoxybut-2-yne
In a Schlenk reactor, a n-butyllithium solution (7.7
mmol in hexane) was added to a 3,3-diethoxypropyne
solution (7 mmol) in THF (5 mL) at room temperature.
After 10 min stirring the reaction mixture was quenched
with dimethylsulfate (7.7 mmol) before hydrolysis with a
saturated NaCl aqueous solution. Further ether extrac-
tion and usual treatments allowed access to 1,1-dieth-
oxybut-1-yne in 65% yield (0.65 g).
3,3-Diethoxyprop-1-yne was prepared according to
the literature [47] and transacetalised into 3,3-dibenzyl-
oxyprop-1-yne, 2-ethynyl-1,3-dioxane or (4R,6R)-2-
ethynyl-4,6-dimethyl-1,3-dioxane as described below.
5.2.1. Transacetalisation of 3,3-diethoxyprop-1-yne:
typical procedure
3
1H NMR: d = 1.23 (t, 6H, J2H = 6.8), 1.86 (d, 3H,
In a Dean–Stark apparatus were placed 3.9 mmol of
paratoluenesulfonic acid and 0.39 mol of benzyl alcohol
in cyclohexane (400 mL). The solution was stirred and
refluxed for 2 h before addition of diethoxypropyne
(78 mmol). The Dean Stark trap was regularly purged
in order to shift the equilibrium, the reaction being mon-
itored by TLC or GC. At completion, after cooling at
room temperature, 6 mL of triethylamine were added
and the remaining solution filtered on alumina. After
elimination of cyclohexane, the propargylic acetals were
purified by distillation, crystallisation or liquid
chromatography.
3
5J1H = 1), 3.54 and 3,73 (A2B2 syst., 4H, J3H = 6.8,
5
2J1H = 9.2), 5.22 (q, 1H, J3H = 1).
5.3. Organometallic starting materials
Organolithium reagents were Chemetall reagents
while Grignard reagents were prepared using conven-
tional methods in ether solution: EtMgBr (2M),
i-PrMgCl (2M), t-BuMgCl (1M), Me3SiCH2MgCl
(1M).
(E)-1-Tributylstannyl-3,3-diethoxyprop-1-ene (1aE)
was obtained by stannylcupration of 3,3-diet-
hoxypropyne and (Z)-1-tributylstannyl-3,3-diethoxy-
prop-1-ene (1aZ) by titanation of the corresponding
alkynylstannane according to our previous described
procedures [37,38] which were also used to obtain the
other vinyltin acetals respectively in the E series (1bE,
1dE) and in the Z series (1bZ, 1cZ and 1fZ). The (E)-
vinyltin acetals 1cE, 1eE and 1fE were obtained by
transacetalisation of 1aE with the appropriate diols [35].
The complete physicochemical characterization of
1aE [48], 1aZ [48] and 1bE [9] has been already reported
5.2.1.1. 3,3-Dibenzyloxyprop-1-yne (bp15 = 97 ꢁC, 15 g,
4
76% yield). 1H NMR: d = 2.62 (d, 1H, J1H = 1.8),
4.65 and 4.80 (A2B2 syst., 4H, J1H = 11.6), 5.48 (d,
2
4
1H, J1H = 1.8), 7,38 (m, 10Harom).; 13C NMR:
d = 67.5 (2C), 74.4, 78.7, 90.5, 127.9 (2C), 128.1 (4C),
128.4 (4C), 137.3 (2C); IR: m = 3285, 3065, 2876, 2125,
1498, 1454, 1200–950, 739, 697 cmꢀ1; MS: m/z
(%) = 161 (MÅ+ –91, 2), 144 (2), 107 (20), 92 (71), 91
(100), 77 (9), 65 (13), 51 (3), 39 (2); elemental analysis
Calc. (%) for C17H16O2 (252.12): C, 80.93; H, 6.39.
Found: C, 81.06; H, 6.39%.

F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
667
and the characterization of the other vinyltin acetals is
given below.
(3JSn–C = 72/76), 138.8, 144.2; 119Sn NMR: d = ꢀ48.6;
IR: m = 1465, 1457, 1376, 1146, 1115, 1079, 980 cmꢀ1
;
MS: organostannyl fragments: m/z (%) = 361
(MÅ+ ꢀ 57, 55), 305 (41), 249 (11), 233 (10), 177 (26),
121 (14); organic fragments: m/z (%) = 127 (100), 101
(10), 73 (14), 55 (47), 29 (9); elemental analysis Calc.
(%) for C19H38O2Sn (416.19): C, 54.70; H, 9.18. Found:
C, 54.79; H, 9.08%.
5.3.1. (E)-2-(2-Tributylstannylethylidene)-1,3-dioxane
(1cE, 87% yield)
1H NMR: d = 0.70–1.10 (m, 15H), 1.15–1.70 (m,
13H), 2.23 (m, 1H), 3.83 (m, 2H), 4.15 (m, 2H), 4.91
3
(dd, 1H, J1H = 4.1, J1H = 0.7, JSn–H = 9.7), 5.98 (dd,
4
4
3
3
3
1H, J1H = 19.3, J1H = 4.1, JSn–H = 42), 6.48 (dd, 1H,
3J1H = 19.3, 4J1H = 0.7, 2JSn–H = 43); 13C NMR:
5.3.5. (E)-(4R,6R)-2-(2-Tributylstannylethylidene)-
4,6-dimethyl-1,3-dioxane (1fE, 82% yield)
1H NMR d = 0.70–1.10 (m, 15H), 1.15–1.70 (m,
19H), 1.87 (ddd, 1H, 3J1H = 6.2, 2J1H = 11.7,
3J1H = 13.3), 4.01 (m, 1H), 4.15 (m, 1H), 5.19 (dd, 1H,
1
d = 9.5 (3C, JSn–C = 332/347), 13.7 (3C), 25.9, 27.3
3
2
(3C, JSn–C = 56), 29.1 (3C, JSn–C = 21), 66.8, 67.0,
102.2 (3JSn–C = 70), 133.6 (1JSn–C = 341/357), 144.1;
MS: organostannyl fragments: m/z (%) = 347
(MÅ+ ꢀ 57, 42), 291 (32), 233 (12), 177 (17); organic frag-
ments: m/z (%) = 113 (100), 87 (11), 55 (10).
4
4
3J1H = 4.4, J1H = 1.1, JSn–H = 6), 5.96 (dd, 1H,
3
3
3J1H = 19.2, J1H = 4.4, JSn–H = 61/64), 6.40 (dd, 1H,
4
2
3J1H = 19.2, J1H = 1.1, JSn–H = 67/70); 13C NMR:
1
5.3.2. (Z)-2-(2-Tributylstannylethylidene)-1,3-dioxane
(1cZ, 87% yield)
d = 9.4 (3C, JSn–C = 331/347), 13.6 (3C), 17.2, 21.8,
3
2
27.3 (3C, JSn–C = 57), 29.0 (3C, JSn–C = 21), 36.9,
67.6, 68.2, 94.8 (3JSn–C = 73), 133.2 (1JSn–C = 345/361),
144.5 (2JSn–C = 21); MS: organostannyl fragments: m/z
(%) = 375 (MÅ+ ꢀ 57, 60), 319 (21), 289 (21), 233 (39),
177 (45), 121 (15); organic fragments: m/z (%) = 141
(100), 99 (4), 97 (4), 69 (4), 32 (5), 28 (33).
1H NMR: d = 0.70–1.10 (m, 15H), 1.15–1.70 (m,
13H), 2.10 (m, 1H), 3.78 (td, 2H, J1H = 12.2,
2
3
2
3J1H = 12.2, J1H = 2.5), 4.15 (ddd, 2H, J1H = 12.2,
3
3
3J1H = 5.0, J1H = 1.3), 4.89 (dd, 1H, J1H = 3.3,
4J1H = 1.3), 6.21 (dd, 1H, J1H = 13.4, J1H = 1.3), 6.47
3
4
(dd, 1H, J1H = 13.4, J1H = 3.3); 13C NMR: d = 11.0
3
3
1
(3C, JSn–C = 336/352), 13.6 (3C), 25.7, 27.4 (3C,
3JSn–C = 55), 29.3 (3C), 66.6 (2C), 101.1 (3JSn–C = 46),
134.3 (1JSn–C = 255), 143.2; IR: m = 2956, 2922, 2872,
2852, 1464, 1377, 1101, 1008, 960, 672 cmꢀ1; MS:
organostannyl fragments: m/z (%) = 403 (MÅ+ ꢀ H, 1),
347 (100), 291 (35), 233 (46), 177 (75), 121 (25); organic
fragments: m/z (%) = 113 (29), 57 (28), 41 (53).
5.3.6. (Z)-(4R,6R)-2-(2-Tributylstannylethylidene)-
4,6-dimethyl-1,3-dioxane (1fZ, 80% yield)
1H NMR: d = 0.70–1.10 (m, 15H), 1.15–1.70 (m,
19H), 1.87 (ddd, 1H, 3J1H = 8, 3J1H = 12.3,
3
3
2J1H = 13.3), 4.0 (m, 1H, J1H = 2.7, J3H = 6.2,
3J1H = 12.3), 4.35 (m, 1H, J3H = 6.7, J1H = 8), 5.15
3
3
3
(dd, 1H, J1H = 4.6, J1H = 1.1), 6.19 (dd, 1H,
4
3J1H = 13.2, J1H = 1.1), 6.50 (dd, 1H, J1H = 13.2,
4
3
5.3.3. (E)-3-Tributylstannyl-1,1-diethoxybut-2-ene
(1dE, 90% yield)
3J1H = 4.6); 13C NMR: d = 11.5 (3C), 14.1 (3C), 17,5,
22.3, 27.8 (3C, JSn–C = 55), 29.5 (3C), 37.2, 68.0, 68.5,
3
1H NMR: d = 0.70–1.70 (m, 33H), 1.94 (d, 3H,
3
4J1H = 1.8, JSn–H = 44/46), 3.50 and 3.63 (A2B2 syst.,
94.7, 134.6, 144.4; IR: m = 2956, 2922, 2872, 2854,
1458, 1375, 1150, 1018, 965, 697 cmꢀ1; MS: organostan-
nyl fragments: m/z (%) = 431 (MÅ+ ꢀ H, 1), 375 (100),
289 (71), 233 (55), 175 (81), 121 (14); organic fragments:
m/z (%) = 141 (16), 69 (58).
2
3
4H, J1H = 9.5, J3H = 7.0), 5.26 (d, 1H, J1H = 6.0,
3
4JSn–H = 8), 5.58 (dq, 1H, J1H = 6.0, J3H = 1.8,
3JSn–H = 61/65); 13C NMR: d = 9.2 (3C, JSn–C = 322/
3
4
1
3
337), 13.6 (3C), 15.3 (2C), 20.1, 27.3 (3C, JSn–C = 54/
57), 29.1 (3C), 60.3 (2C), 96.9 (3JSn–C = 66/69), 137.6,
145.4; MS: organostannyl fragments: m/z (%) = 378
(MÅ+ ꢀ 56, 22), 331 (18), 275 (4), 235 (4), 177 (13), 165
(13); organic fragments: m/z (%) = 143 (100), 99 (30),
41 (6), 29 (13).
5.4. Reaction of vinyltin acetals with organocopper
reagents in the presence of boron trifluoride: typical
experimental procedure
In a flame dried Schlenk reactor, a solution of organ-
olithium or organomagnesium reagent (2.2 mmol) was
added dropwise at ꢀ30 ꢁC to a stirred copper cyanide
suspension (1.19 g, 2.2 mmol) in anhydrous ether (previ-
ously degassed at ꢀ50 ꢁC) until an homogeneous solu-
tion was obtained (about 30 min). The latter was
cooled at ꢀ78 ꢁC before addition of boron trifluoride
etherate (0.26 mL, 2.2 mmol), further stirring for 30
min and subsequent addition of vinyltin acetal (0.7
mmol in 2 mL ether). The reaction mixture was stirred
5.3.4. (E)-(4R,5R)-2-(2-Tributylstannylethylidene)-
4,5-dimethyl-1,3-dioxolane (1eE, 92% yield)
1H NMR: d = 0.70–1.05 (m, 15H), 1.15–1.70 (m,
18H), 3.50–3.70 (m, 2H), 5.24 (dd, 1H, J1H = 5.9,
3
4
3
4J1H = 0.6, JSn–H = 4.0), 5.97 (dd, 1H, J1H = 19.0,
3
3
3J1H = 5.9, JSn–H = 58/60), 6.47 (dd, 1H, J1H = 19.0,
2
4J1H = 0.6, JSn–H = 64/67); 13C NMR: d = 9.3 (3C,
1JSn–C = 332/347), 13.5 (3C), 16.8, 17.0, 26.6 (3C, JSn–
3
2
C = 54/57), 28.9 (3C, JSn–C = 21), 78.1, 79.7, 104.5

668
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
1
over 3 h and allowed to warm up to ꢀ50 ꢁC for hydro-
lysis (aqueous NaHCO3 solution). After ether extraction
(3 · 20 mL) and usual treatments, the crude products
were chromatographed on silica gel using hexane–trieth-
ylamine (98/2) as eluent.
When reactions were performed in order to examine
the influence of the order of addition of the reagents,
two separate solutions were prepared in two Schlenk
tubes and one was cannulated in the other at low tem-
perature as mentioned in the Table 2.
Isomer 2bE: meaningful signals: H NMR: d = 4.88
3 3 3
(m, 1H, J1H ꢂ J1H ꢂ 12.5), 6.05 (d, 1H, J1H = 12.5);
13C NMR: d = 64.9, 109.7, 142.5.
5.5.3. 3-Tributylstannyl-1-ethoxyhept-1-ene 2c
MS: organostannyl fragments: m/z (%) = 432 (MÅ+,
1), 403 (7), 375 (21), 291 (44), 235 (100), 179 (99), 121
(36); organic fragments: m/z (%) = 141 (51), 95 (20), 85
(44), 57 (91), 41 (19), 29 (30); IR: m = 2957, 2930, 2870,
2860, 1645, 1378, 1113; elemental analysis Calc. (%)
for C21H44OSn (431.28): C, 58.48; H, 10.28. Found: C,
58.22; H, 10.29%.
5.5. Characterization of a-substituted
c-alkoxyallylstannanes
Isomer 2cZ: 1H NMR: d = 0.70–1.05 (m, 18H), 1.10–
3
1.80 (m, 21H), 2.44 (m, 1H), 3.72 (q, 2H, J3H = 6.9),
3
4.35 (dd, 1H, J1H = 6.2, J1H = 10.8, JSn–H = 20.2),
3
3
5.5.1. 3-Tributylstannyl-1-ethoxybut-1-ene 2a
MS: organostannyl fragments: m/z (%) = 390 (MÅ+,
1), 361 (2), 333 (13), 291 (29), 235 (69), 179 (100), 121
(30); organic fragments: m/z (%) = 99 (56), 71 (64), 43
(14), 41 (12), 29 (10).
3
4
4
5.77 (dd, 1H, J1H = 6.2, J1H = 1.0, JSn–H = 20.1); 13C
1
NMR: d = 8.9 (3C, JSn–C = 283/296), 13.8 (3C), 14.1,
15.3, 22.6, 23.4 (1JSn–C = 296/310), 27.6 (3C, JSn–
3
2
C = 52/53), 29.3 (3C, JSn–C = 19), 32.8, 33.2, 67.2,
111.8 (2JSn–C = 42), 140.4 (3JSn–C = 45).
1
Isomer 2aZ: H NMR: d = 0.70–1.60 (m, 33H), 2.42
(ddq, 1H, J1H = 10.7, J3H = 7.6, J1H = 1.1), 3.71 (q,
Isomer 2cE: 1H NMR: d = 0.70–1.05 (m, 18H), 1.10–
1.80 (m, 21H), 1.93 (m, 1H), 3.65 (q, 2H, J3H = 7.0),
3
3
4
3
3
2H, J3H = 7.0), 4.38 (dd, 1H, J1H = 10.7, J1H = 6.1,
3
3
3
4.88 (dd, 1H, J1H = 12.3, J1H = 10.6, JSn–H = 22.0),
3
3
3
4
3JSn–H = 20.2), 5.72 (dd, 1H, J1H = 6.1, J1H = 1.1,
6.04 (d, 1H, J1H = 12.3, JSn–H = 19.5); 13C NMR:
3
4
4JSn–H = 21.5); 13C NMR: d = 8.5 (3C, JSn–C
=
1
1
d = 8.8 (3C, JSn–C = 285/298), 13.7 (3C), 14.0, 15.9,
254/297), 13.4 (3C), 15.0, 16.3, 18.4 (2JSn–C = 19.5),
3
22.5, 25.7, 27.4 (3C, JSn–C = 26), 29.2 (3C, JSn–C
2
=
3
2
27.3 (3C, JSn–C = 53), 29.1 (3C, JSn–C = 21), 67.0,
113.3 (2JSn–C = 41), 139.4 (3JSn–C = 43/45); 119Sn
NMR: d = ꢀ16.5.
16), 32.2 (3JSn–C = 40), 33.3 (2JSn–C = 13), 64.9, 110.0
(2JSn–C = 37), 142.2 (3JSn–C = 52).
1
Isomer 2aE: H NMR: d = 0.70–1.60 (m, 33H), 1.97
5.5.4. 3-Tributylstannyl-1-ethoxy-4-methylpent-1-ene 2d
MS: organostannyl fragments: m/z (%) = 418 (MÅ+,
1), 389 (7), 361 (49), 291 (46), 235 (77), 179 (74); organic
fragments: m/z (%) = 127 (100), 81 (49), 43 (80); IR:
m = 2956, 2925, 2872, 2360, 1648, 1464, 1380, 1110,
668; HRMS: MÅ+ = 418.2248 /416.2249 /414.2259 for
120Sn, 118Sn and 116Sn; elemental analysis Calc. (%) for
C20H42OSn (417.26): C, 57.57; H, 10.15. Found: C,
57.52; H, 10.13%.
3
4
(ddq, 1H, J3H = 3J1H = 8.8, J1H = 1.3), 3.71 (q, 2H,
3J3H = 7.2), 5.06 (dd, 1H, J1H = 12.5, J1H = 8.8,
3
3
3JSn–H = 22.2), 6.02 (dd, 1H, J1H = 12.5, J1H = 1.3,
3
4
4JSn–H = 19); 13C NMR: d = 8.2 (3C, JSn–C = 268/299),
13.4 (3C), 14.6, 16.2, 18.6, 27.2 (3C, JSn–C = 51), 28.9
1
3
(3C, JSn–C = 20), 64.6, 111.6 (2JSn–C = 36), 141.3 (3JSn–
2
C = 49); 119Sn NMR: = ꢀ18.5.
1
5.5.2. 3-Tributylstannyl-1-ethoxypent-1-ene 2b
Isomer 2dZ: H NMR: d = 0.60–1.70 (m, 36H), 1.80
(m, 1H), 2.35 (ddd, 1H, J1H = 11.4, J1H = 7.5,
3
3
MS: organostannyl fragments: m/z (%) = 375
(MÅ+ ꢀ 29, 1), 347 (5), 291 (12), 235 (40), 179 (62), 121
(15); organic fragments: m/z (%) = 113 (100), 85 (56),
67 (30), 57 (42), 43 (34); IR: m = 2956, 2924, 2872,
1649, 1465, 1378, 1111, 668; HRMS: MÅ+ = 404.2071 /
402.2076 / 400.2073 for 120Sn, 118Sn and 116Sn; elemental
analysis Calc. (%) for C19H40OSn (403.23): C, 56.59; H,
10.00. Found: C, 56.41; H, 9.74%.
4J1H = 1.0), 3.65 (q, 2H, J3H = 7.3), 4.33 (dd, 1H,
3
3J1H = 6.5, J1H = 11.4, JSn–H = 20.5), 5.72 (dd, 1H,
3
3
3J1H = 6.5, J1H = 1.0, JSn–H = 21.1); 13C NMR:
4
4
1
d = 9.8 (3C, JSn–C = 283/296), 13.7 (3C), 15.3, 23.0
(3JSn–C = 34), 24.0 (3JSn–C = 31), 27.6 (3C, JSn–C = 56),
3
29.3 (3C, JSn–C = 20), 31.2, 33.4 (1JSn–C = 300/315),
2
67.2, 109.5 (2JSn–C = 40), 140.8 (3JSn–C = 47).
1
1
Isomer 2bZ: H NMR: d = 0.60–1.70 (m, 35H), 2.32
(m, 1H, J1H = 11.0, J1H = 6.1, J1H = 8.8, J1H = 1.0),
Isomer 2dE: meaningful signals: H NMR: d = 4.88
3
3
3
4
3
3
3
(m, 1H, J1H ꢂ J1H ꢂ 12.0), 6.05 (d, 1H, J1H = 12.0).
3
3.65 (q, 2H, J3H = 7.1), 4.30 (dd, 1H, J1H = 6.1,
3
3
3
3J1H = 11.0, JSn–H = 20.5), 5.71 (dd, 1H, J1H = 6.1,
5.5.5. 3-Tributylstannyl-1-ethoxy-4,4-dimethylpent-
1-ene 2e
MS: organostannyl fragments: m/z (%) = 432 (MÅ+,
3), 403 (15), 375 (72), 291 (47), 235 (58), 177 (56); organ-
ic fragments: m/z (%) = 141 (100), 95 (76), 43 (61); IR:
m = 2960, 2953, 2935, 2924, 1646, 1379, 1111, 663;
4
4J1H = 1.0, JSn–H = 21); 13C NMR: d = 8.7 (3C,
1JSn–C = 283/296), 13.4 (3C), 14.9 (3JSn–C = 46), 15.0,
25.4 (1JSn–C = 295/311), 26.2 (2JSn–C = 16), 27.1 (3C,
3JSn–C = 47), 29.2 (3C, JSn–C = 20), 67.0, 111.2
2
(2JSn–C = 41), 140.3 (3JSn–C = 45).

F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
669
3
2.52 (ddq, 1H, J3H = 7.6, J1H = 10.8, J1H = 0.9,
3
4
HRMS: MÅ+ = 432.2473 /430.2393 /428.2460 for 120Sn,
118Sn and 116Sn; elemental analysis Calc. (%) for
C21H44OSn (431.28): C, 58.48; H, 10.28. Found: C,
58.65; H, 10.15%.
3
3
2JSn–H = 60), 4.45 (dd, 1H, J1H = 10.8, J1H = 6.0,
2
3JSn–H = 20), 4.7 and 4.77 (AB syst., 2H, J1H = 12.7),
3
4
5.85 (dd, 1H, J1H = 6.0, J1H = 0.9, JSn–H = 20), 7.2-
4
1
1
Isomer 2eZ: H NMR: d = 0.60–1.60 (m, 39H), 2.49
(dd, 1H, J1H = 12.0, J1H = 1.0), 3.65 (q, 2H,
7.4 (m, 5H); 13C NMR: d = 8.7 (3C, JSn–C = 298/285),
13.7 (3C), 16.6, 18.7, 27.5 (3C, JSn–C = 54), 29.3 (3C,
3
4
3
3J3H = 7.0), 4.39 (dd, 1H, J1H = 6.0, J1H = 12.0,
2JSn–C = 20), 73.5, 114.6 (2JSn–H = 41), 127.4-128.3
(5C), 138.0, 139.4 (3JSn–C = 44); 119Sn NMR:
d = ꢀ15,7; IR: m = 3029, 2924, 2956, 2870, 1648, 1457,
1420, 1050-1125, 694-730; MS: organostannyl frag-
ments: m/z (%) = 395 (3, MÅ+ ꢀ 57), 361 (4, MÅ+ ꢀ 91),
291 (19), 235 (32), 179 (37), 121 (10); organic fragments:
m/z (%) = 91 (100), 65 (8).
3
3
3JSn–H = 21), 5.74 (dd, 1H, J1H = 6.0, J1H = 1.0,
3
4
4JSn–H = 21.1); 13C NMR: d = 10.6 (3C, JSn–C
281/290), 13.6 (3C), 15.3, 27.6 (3C, JSn–C = 58), 29.6
=
1
3
2
3
(3C, JSn–C = 20), 30.7 (3C, JSn–C = 26), 33.7, 39.8
(1JSn–C = 291/310), 67.1, 108.4 (2JSn–C = 39), 141.1
(3JSn–C = 48).
1
Isomer 2eE: meaningful signals: H NMR: d = 3.45
(q, 2H, J3H = 7.0), 4.88 (dd, 1H, J1H = 10.6,
3J1H = 12.3, JSn–H = 22), 6.05 (d, 1H, J1H = 12.3,
3
3
3
3
5.5.9. (Z)-1-Benzyloxy-3-tributylstannyl-4,4-
dimethylpent-1-ene 2iZ
4JSn–H = 19).
1H NMR: d = 0.7–0.95 (m, 15H), 0.95 (9H), 1.2–1.7
(m, 12H), 2.65 (dd, 1H, J1H = 12.4, J1H = 0.6,
3
4
3
3
2JSn–H = 64), 4.52 (dd, 1H, J1H = 12.4, J1H = 6.2,
5.5.6. (Z)-3-Tributylstannyl-1-ethoxy-4-
trimethylsilylbut-1-ene 2fZ
3JSn–H = 22/27), 4.71 and 4.79 (AB syst., 2H,
3
4
2J1H = 12.5), 5.92 (dd, 1H, J1H = 6.2, J1H = 0.6,
4JSn–H = 19), 7.20–7.40 (m, 5H); 13C NMR: d = 10.7
(3C, 1JSn–C = 283/295), 13.7 (3C), 27.6 (3C,
3JSn–C = 57), 29.3 (3C, 2JSn–C = 13), 30.6 (3C,
3JSn–C = 26), 33.8 (2JSn–C = 13), 39.9 (1JSn–C = 297/
312), 73.4, 109.5 (2JSn–C = 38), 127.3–128.3 (5C), 138.1,
141.1 (3JSn–C = 48); 119Sn NMR: d = ꢀ29,0; IR:
m = 3029, 2956, 2927, 2871, 1646, 1455, 1390, 1119,
1096, 732, 695; MS: organostannyl fragments: m/z
(%) = 437 (3, M ꢀ 57), 403 (7, M ꢀ 91), 291(28), 235
(41), 179 (34), 121 (7); organic fragments: m/z
(%) = 91(100); elemental analysis Calc. (%) for
C26H46OSn (493.35): C, 63.30; H, 9.40. Found: C,
63.23; H, 9.58%.
1H NMR (C6D6, 300 K): d = 0.13 (s, 9H), 0.80–1.80
(m, 32H), 2.86 (tdd, 1H, J2H = 7.2, J1H = 11.1,
3
3
3
4J1H = 1.0), 3.45 (q, 2H, J3H = 7.1), 4.43 (dd, 1H,
3
3
3J1H = 6.0, J1H = 11.1, JSn–H = 20.2), 5.53 (dd, 1H,
3J1H = 6.0, 4J1H = 1.0, 4JSn–H = 22.4); 13C NMR
1
(C6D6, 300 K): d = ꢀ0.7 (3C), 9.3 (3C, JSn–C
=
276/289), 13.9 (3C), 15.5, 17.7 (1JSn–C = 302/317), 21.1
(2JSn–C = 28), 28.0 (3C, 3JSn–C = 51), 29.8 (3C,
2JSn–C = 19), 67.3, 114.0 (2JSn–C = 42), 140.0 (3JSn–
C = 48); MS: organostannyl fragments: m/z (%) = 433
(MÅ+ ꢀ 29, 11), 291 (26), 235 (63), 179 (66), 177 (18),
121 (23); organic fragments: m/z (%) = 171 (95), 143
(100), 73 (81), 45 (6); IR: m = 1640, 1460, 1450, 1375,
1240, 1105, 855, 835; HRMS: MÅ+ (very
weak) = 462.2350 for 120Sn; meaningful ions: 171.1207
(C9H19OSi)+ and 291.1163 (C12H27Sn)+ for 120Sn.
5.5.10. 3-(3-Tributylstannylpent-1-en-1-yloxy)propan-
1-ol 2j
MS: organostannyl fragments: m/z (%) = 377
(MÅ+ ꢀ 57, 6), 291 (32), 235 (83), 179 (100), 121 (38); or-
ganic fragments: m/z (%) = 143 (35), 85 (73), 69 (16), 67
(20), 59 (10), 57 (36), 55 (11), 43 (36), 41 (43), 31 (42), 29
(32); IR: m = 3350, 1650, 1638, 1468, 1418, 1075, 965, 740.
Isomer 2jZ: H NMR: d = 0.70–1.05 (m, 12H), 1.10–
1.80 (m, 20H), 1.70–2.0 (m, 2H), 2.18–2.48 (m, 1H),
3.70–3.90 (m, 4H), 4.39 (dd, 1H, 3J1H = 6.1,
5.5.7. (Z)-3-Tributylstannyl-1-ethoxy-4-
(dimethylphenylsilyl)but-1-ene 2gZ
3
1H NMR: d = 0.23 (s, 6H), 0.77 (d, 2H, J1H = 7.9),
0.70–1.00 (m, 12H), 1.10–1.70 (m, 18H), 2.59 (m, 1H),
3
3.70 (q, 2H, J3H = 7.0), 4.30 (dd, 1H, J1H = 6.1,
3
1
3
3
3J1H = 11.0, JSn–H = 20), 5.63 (dd, 1H, J1H = 6.1,
4
4J1H = 0.75, JSn–H = 22.4), 7.28–7.38 and 7.40–7.55
(2m, 5H) ; 13C NMR: d = ꢀ1.2 (2C), 8.8 (3C, JSn–C
=
1
3
3
3J1H = 11.1, JSn–H = 19.9), 5.8 (dd, 1H, J1H = 6.1,
277/290), 13.6 (3C), 15.4, 16.9, 19.6 (2JSn–C = 27), 27.5
4J1H = 0.7, JSn–H = 20.8); 13C NMR: d = 9.0 (3C,
4
3
2
(3C, JSn–C = 50/53), 29.2 (3C, JSn–C = 19.5), 67.0,
113.5 (2JSn–C = 43.5), 127.4 (2C), 128.7 (2C), 133.2,
139.4 (3JSn–C = 46/48), 140.5; 119Sn NMR: d = ꢀ15.8.
1JSn–C = 284/297), 13.7 (3C), 25.9, 26.5, 27.6 (3C, JSn–
3
2
C = 53), 29.3 (3C, JSn–C = 20), 32.1, 60.8, 69.9, 112.2
(2JSn–C = 40), 140.7 (3JSn–C = 51).
1
Isomer 2jE: H NMR: meaningful signals: d = 4.92
(dd, 1H, J1H = 12.6, J1H = 10.1, JSn–H = 23.1), 6.08
(d, 1H, J1H = 12.6, JSn–H = 19.3); 13C NMR: d = 8.9
(3C, JSn–C = 286/300), 13.7 (3C), 25.9, 28.1, 27.6 (3C,
3
3
3
5.5.8. (Z)-1-Benzyloxy-3-tributylstannylbut-1-ene 2hZ
1H NMR: d = 0.7–0.9 (m, 6H), 0.85 (t, 9H,
3
4
3J2H = 7.3), 1.1–1.7 (m, 12H), 1.29 (d, 3H, J1H = 7.6),
3
1

670
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
2
3JSn–C = 53), 29.3 (3C, JSn–C = 20), 32.5, 60.9, 67.7,
Isomer 2mE: 1H NMR: d = ꢀ0.05–0.15 (m, 11H),
110.3 (2JSn–C = 40), 142.4 (3JSn–C = 51).
3
0.75–1.75 (m, 33H), 3.68 (q, 2H, J3H = 7.0), 5.16 (d,
1H, 3J1H = 12.5, 3JSn–H = 20/23), 5.82 (d, 1H,
4
5.5.11. 3-(3-Tributylstannyl-4-methylpent-1-en-1-
yloxy)propan-1-ol 2k
3J1H = 12.5, JSn–H = 21).
MS: organostannyl fragments: m/z (%) = 348 (MÅ+,
2), 389 (14), 335 (1), 291 (36), 235 (79), 179 (100),
121 (47); organic fragments: m/z (%) = 157 (25), 99
(37), 83 (17), 81 (97), 59 (10), 57 (25), 55 (20), 43
(98), 41 (37), 31 (49), 29 (29), 27 (12); IR: m = 3340,
1648, 1632, 1462, 1418, 1373, 1362, 1105, 1070, 960,
925, 875, 865.
5.5.14. (2R,3R)-3-(3-Tributylstannylhept-1-en-1-
yloxy)butan-2-ol 2n
MS: organostannyl fragments: m/z (%) = 419
(MÅ+ ꢀ 57, 5), 403 (MÅ+ ꢀ 73, 8), 291 (33), 269 (22),
251 (57), 235 (87), 213 (13), 179 (100), 121 (34); organic
fragments: m/z (%) = 185 (12), 113 (52), 95 (41), 83 (16),
73 (37), 69 (12), 57 (81), 55 (59), 45 (20), 43 (16), 41 (35),
29 (23), 27 (16); IR: m = 3456, 1651, 1465, 1377, 1289,
1265, 1106, 961, 927 876.
Isomer 2nZ: Major diastereomer: 1H NMR: d = 0.75–
0.95 and 1.15–1.65 (2m, 42H), 1.80–2.10 (m, 1H), 2.41
3
(bd, 1H, J1H = 3.1), 3.35–3.50 (m, 1H), 3.55–3.75 (m,
Isomer 2kZ: 1H NMR: d = 0.60–1.00 (m, 15H), 1.10–
1.60 (m, 19H), 1.70-2.00 (m, 2H), 2.29 (ddd, 1H,
3
4
3J1H = 12.3, J1H = 6.5, J1H = 1.0), 3.60–3.85 (m, 4H),
3
4.35 (dd, 1H, J1H = 6.5, J1H = 12.3, JSn–H = 20.2),
5.74 (dd, 1H, J1H = 6.5, J1H = 1.0, JSn–H = 20.5); 13C
3
3
3
4
4
1
3
3
1H), 4.36 (dd, 1H, J1H = 6.1, J1H = 11.2, JSn–H = 20),
3
NMR: d = 9.8 (3C, JSn–C = 285/300), 13.7 (3C), 23.0,
3
2
3
4
24.0, 27.6 (3C, JSn–C = 58), 29.4 (3C, JSn–C = 20),
31.7, 32.5, 33.6 (1JSn–C = 295/309), 60.7, 69.9, 110.1
(2JSn–C = 43), 140.7 (3JSn–C = 51).
5.84 (d, 1H, J1H = 6.1, JSn–H = 20); 13C NMR: d = 8.7
(3C, JSn–C = 284/297), 13.3, 13.4 (3C), 18.1, 22.2, 27.3
1
3
2
(3C, JSn–C = 52), 29.0 (3C, JSn–C = 20), 32.0, 32.6,
70.6, 82.1, 111.9 (2JSn–C = 40), 139.4 (3JSn–C = 46); 119Sn
NMR: d = ꢀ19.3.
1
Isomer 2kE: H NMR: meaningful signals: d = 4.92
(dd, 1H, J1H = 12.3, J1H = 10.7, JSn–H = 24.0), 6.08
3
3
3
(d, 1H, J1H = 12.3, JSn–H = 17.3); 13C NMR: d = 9.7
(3C, JSn–C = 285/299), 13.7 (3C), 22.7, 23.8, 27.6 (3C,
Isomer 2nE: Major diastereomer: H NMR: mean-
3
4
1
1
ingful signals: d = 5.04 (dd, 1H, 3J1H = 10.8,
3JSn–C = 54), 29.4 (3C, JSn–C = 20), 31.3, 32.6, 36.0
3J1H = 12.0), 5.91 (d, 1H, J1H = 12.0); 13C NMR:
2
3
(1JSn–C = 308/323), 60.7, 67.6, 108.1 (2JSn–C = 34),
143.0 (3JSn–C = 55).
d = 8.5 (3C, JSn–C = 285/298), 13.3, 13.4 (3C), 18.0,
1
3
2
22.1, 27.3 (3C, JSn–C = 52), 28.9 (3C, JSn–C = 20),
32.0, 32.7, 70.9, 80.9, 113.1 (2JSn–C = 37), 140.7
(3JSn–C = 54); 119Sn NMR: d = ꢀ20.9.
5.5.12. (Z)-3-(3-Tributylstannyl-4,4-dimethylpent-1-en-
1-yloxy)propan-1-ol 2lZ
5.5.15. (2R,4R)-4-(3-Tributylstannylbut-1-en-1-
yloxy)pentan-2-ol 2o
1H NMR: d = 0.60-1.00 (m, 15H), 0.89 (s, 9H),
1.10–1.60 (m, 12H), 1.79 (qt, 2H, J4H = 5.6), 2.42
3
Isomer 2oE: 1H NMR: d = 0.70–1.70 (m, 38H), 1.88–
2.27 (m, 1H), 2.20 (bd, 1H, J1H = 4.6), 3.85–4.20 (m,
3
(dd, 1H, J1H = 12.3, J1H = 1.0), 3.60–3.85 (m, 4H),
4
3
3
3
4.42 (dd, 1H, J1H = 6.4, J1H = 12.3, JSn–H = 22.8),
3
3
2H), 5.19 (dd, 1H, J1H = 8.4, J1H = 12.2), 5.8 (dd,
3
3
5.74 (dd, 1H, J1H = 6.4, J1H = 1.0, JSn–H = 19.2);
13C NMR: d = 10.2 (3C, JSn–C = 288/301), 13.3 (3C),
27.2 (3C, JSn–C = 61), 28.9 (3C, JSn–C = 20), 30.2
4
4
3
4
1H, J1H = 12.2, J1H = 1.4); 13C NMR: d = 8.6 (3C,
1
1JSn–C = 286/300), 13.7 (3C), 17.9 (2JSn–C = 16), 18.8
3
2
(1JSn–C = 297/311), 20.0, 23.7, 27.5 (3C, JSn–C = 53),
3
3
2
29.3 (3C, JSn–C = 20), 44.9, 64.7, 74.1, 114.7
(3C, JSn–C = 29), 32.0, 33.4, 39.5, 60.5, 70.0, 108.8
(2JSn–C = 40), 140,8; IR: m = 3333, 2956, 2930, 2872,
1646, 1465, 1375, 1125, 1097, 798, 668; MS:
organostannyl fragments: m/z (%) = 461 (MÅ+, 4), 403
(40), 345 (10), 291 (72), 235 (98), 177 (89), 121 (20);
organic fragments: m/z (%) = 171 (100), 113 (48),
95(93).
(2JSn–C = 37), 140.2 (3JSn–C = 50).
Isomer 2oZ: Major diastereomer: 1H NMR: meaning-
ful signals: d = 4.40 (dd, 1H, 3J1H = 6.1, 3J1H = 11.0), 5.73
(dd, 1H, J1H = 6.1, J1H = 1.1); 13C NMR: = 8.7 (3C),
3
4
3
13.7 (3C), 16.7, 18.8, 20.5, 23.9, 27.5 (3C, JSn–C = 53),
29.3 (3C, 2JSn–C = 20), 45.4, 64.6, 74.8, 114.4, 198.5.
1
Minor diastereomer: meaningful signals: H NMR:
3
3
d = 4.51 (dd, 1H, J1H = 6.2, J1H = 9.2), 5.78 (dd, 1H,
3J1H = 6.2, J1H = 1.1).
4
5.5.13. 3-Tributylstannyl-1-ethoxy-3-
(trimethylsilylmethyl)but-1-ene 2m
(chromatographed on C-18 silica gel phase [49] using
MeCN/CH2Cl2 80/20 as eluent).
5.5.16. (2R,4R)-4-(3-Tributylstannylhept-1-en-1-
yloxy)pentan-2-ol 2p
MS: organostannyl fragments: m/z (%) = 490 (MÅ+,
<1), 433 (8), 403 (23), 321 (51), 291 (55), 235 (99), 179
(99), 121 (41); organic fragments: m/z (%) = 113 (84),
95 (40), 69 (59), 57 (100), 55 (17), 45 (80), 43 (27), 41
Isomer 2mZ: 1H NMR: d = ꢀ0.05–0.10 (m, 11H),
3
0.70–1.70 (m, 33H), 3.65 (q, 2H, J3H = 7.2), 4.31 (d,
3
3
3
1H, J1H = 6.8, JSn–H = 31), 5.58 (d, 1H, J1H = 6.8,
4JSn–H = 24).

F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
671
1
Minor diastereomer: meaningful signals: H NMR:
(33), 29 (20); IR: m = 3380, 1646, 1465, 1460, 1376, 1155,
1115, 1080, 960; elemental analysis Calc. (%) for
C24H50O2Sn (489.36): C, 58.90; H, 10.30. Found: C,
58.88; H, 10.55%. [a]D = +117.5 (c = 1.02 in CHCl3).
Isomer 2pZ: Major diastereomer: 1H NMR:
d = 0.65–1.00 (m, 18H), 1.10–1.75 (m, 26H), 2.14 (bd,
3
3
d = 4.35 (dd, 1H, J1H = 10, J1H = 6.2), 5.81 (dd, 1H,
4
3J1H = 6.2, J1H = 0.7); 13C NMR: d = 9.6 (3C), 13.24
(3C), 44.8, 64.6, 75.3, 109.3 (2JSn–C = 39), 140.0
(3JSn–C = 47).
1
Isomer 2rE: meaningful signals: H NMR: d = 4.96
(dd, 1H, J1H = 12.2, J1H = 11.8), 5.87 (dd, 1H,
3
3
3
3
3
1H, J1H = 4.3), 2.41 (m, 1H, J1H = 6.1, J1H = 9.2,
4
4
3J1H = 11.4, J1H = 0.7), 3.85-4.15 (m, 2H), 4.40 (dd,
3J1H = 12.2, J1H = 0.7); 13C NMR: = 9.6 (3C), 13.6
(3C), 64.7, 74.0, 110.6, 141.6.
3
1H, J1H = 6.1, J1H = 11.4, JSn–H = 19.7), 5.8 (dd,
3
3
3
4
4
1H, J1H = 6.1, J1H = 0.7, JSn–H = 18.6); 13C NMR:
1
d = 8.9 (3C, JSn–C = 284/297), 13.8 (3C), 14.1, 20.4,
5.5.19. (2R,4R)-4-(3-Tributylstannyl-4 4-dimethylpent-
1-en-1-yloxy)pentan-2-ol 2s
22.4, 23.3 (1JSn–C = 296/309), 23.8, 27.6 (3C,
3JSn–C = 53), 29.1 (3C, 2JSn–C = 20), 32.7, 33.0
(2JSn–C = 15.6), 45.2, 64.6, 74.8, 112.9 (2JSn–C = 41),
139.3 (3JSn–C = 46); 119Sn NMR: d = ꢀ20.7.
MS: organostannyl fragments: m/z (%) = 490 (MÅ+–
BuÅ, <1), 433 (7), 403 (23), 321 (41), 291 (47), 235 (75),
179 (81), 121 (33); organic fragments: m/z (%) = 199
(7), 113 (77), 95 (34), 85 (10), 69 (42), 57 (15), 55 (14),
45 (58), 43 (100), 41 (29), 29 (15); IR: m = 3387, 1646,
1464, 1376, 1342, 1155, 1114, 1090, 960, 737; HRMS:
MÅ+–BuÅ (C4H9)Å = 433.2138 / 431.2087 / 429.2093 for
120Sn, 118Sn and 116Sn; elemental analysis Calc. (%) for
C24H50O2Sn (489.36): C, 58.90; H, 10.30. Found: C,
58.65; H, 10.22%.
1
Minor diastereomer: meaningful signals: H NMR:
3
3
d = 4.38 (dd, 1H, J1H = 6.1, J1H = 11.1), 5.85 (d, 1H,
3J1H = 6.1).
Isomer 2pE: meaningful signals: H NMR: d = 5.05
(dd, 1H, J1H = 12.1, J1H = 10.7), 5.93 (d, 1H,
3J1H = 12.1).
1
3
3
5.5.17. (2R,4R)-4-(3-Tributylstannylprop-1-en-1-
yloxy)pentan-2-ol 2qZ
Isomer 2sZ: Major diastereomer: 1H NMR: d = 0.55–
1.0 (m, 18H), 0.92 (s, 9H), 1.15–1.75 (m, 17H), 2.11 (bd,
3
1H, J1H = 4.4), 2.52 (dd, 1H, J1H = 12.4, J1H = 0.6,
3
4
1H NMR: d = 0.65–1.05 and 1.10–1.75 (2m, 35H), 1.65
(m, 2H), 2.20 (bd, 1H, 3J1H = 4.2), 3.85–4.20 (m, 2H), 4.52
(td, 1H, 3J1H = 6.1, 3J2H = 9.1), 5.82 (td, 1H, 3J1H = 6.1,
3
3JSn–H = 62), 3.9-4.2 (m, 2H), 4.53 (dd, 1H, J1H = 6.1,
3
3
3J1H = 12.4, JSn–H = 22), 5.85 (dd, 1H, J1H = 6.1,
4J2H = 1.0, JSn–H = 20); 13C NMR: d = 6.0, 9.3 (3C,
4J1H = 0.6, JSn–H = 17); 13C NMR: d = 10.6 (3C,
4
4
1JSn–C = 298/312), 13.7 (3C), 20.6, 23.8, 27.4 (3C, JSn–
1JSn–C = 288/300), 13.7 (3C), 20.6, 24.0, 27.7 (3C,
3
2
2
3
C = 54), 29.0 (3C, JSn–C = 20), 45.0, 64.6, 75.0, 106.1
3JSn–C = 57), 29.3 (3C, JSn–C = 19), 30.6 (3C, JSn–
C = 26), 34 (2JSn–C = 13), 39.8 (1JSn–C = 298/310), 45.3,
64.5, 74.8, 109.7 (2JSn–C = 38), 140.2 (3JSn–C = 48);
119Sn NMR: d = ꢀ29.2.
(2JSn–C = 46), 140.1 (3JSn–C = 45); MS: organostannyl
fragments: m/z (%) = 377 (MÅ+ ꢀ BuÅ ꢀ 57, 20), 321
(56), 291 (45), 235 (79), 179 (100), 121 (35); organic frag-
ments: m/z (%) = 69 (20), 57 (36), 45 (62), 41 (19), 29
(14); [a]D = ꢀ3.2 (c = 1.017 in CHCl3).
Minor diastereomer:1H NMR: meaningful signals:
d = 2.17 (bd, 1H, 3J1H = 4.6), 2.48 (dd, 1H,
4
3J1H = 11.9, J1H = 0.6), 3.9-4.2 (m, 2H), 4.47 (dd, 1H,
3
3
5.5.18. (2R,4R)-4-(3-Tributylstannyl-4-methylpent-1-en-
1-yloxy)pentan-2-ol 2r
3J1H = 6.2, J1H = 11.9, JSn–H = 21), 5.91 (dd, 1H,
3J1H = 6.2, J1H = 0.6); 13C NMR: d = 10.7 (3C), 13.7
4
3
MS: organostannyl fragments: m/z (%) = 476 (MÅ+–
BuÅ, <1), 419 (8), 389 (24), 321 (47), 291 (52), 235 (92),
179 (96), 121 (39); organic fragments: m/z (%) = 99
(91), 81 (34), 69 (50), 57 (17), 55 (16), 45 (74), 43 (100),
41 (32), 29 (17); IR: m = 3360, 1646, 1465, 1376, 1155,
1084; elemental analysis Calc. (%) for C23H48O2Sn
(475.34): C, 58.12; H, 10.18. Found: C, 57.66; H, 10.35%.
Isomer 2rZ: Major diastereomer: 1H NMR: d = 0.55–
(3C), 20.7, 23.7, 27.7 (3C, JSn–C = 57), 29.3 (3C,
2JSn–C = 19), 30.7 (3C), 33.9, 40.0 (1JSn–C = 297/310),
44.9, 64.6, 75.4, 109.7, 140.4 (3JSn–C = 48); 119Sn
NMR: d = ꢀ28.1.
1
Isomer 2sE: H NMR: meaningful signals: d = 1.89
3
(d, 1H, J1H = 12.5), 2.31 (bd, 1H, J1H = 4.4), 3.9–4.2
3
3
(m, 2H), 5.1 (dd, 1H, J1H = 12.5, J1H = 12.3,
3
3
4
3JSn–H = 21), 5.92 (d, 1H, J1H = 12.3, JSn–H = 18) ;
3
1.00 and 1.1–1.65 (2m, 41H), 1.79 (qd, 1H, J1H = 7.5,
3
13C NMR: d = 10.5 (3C), 13.7 (3C), 20.1, 23.6, 27.7
3J3H = 7.2), 2.09 (bs, 1H), 2.23 (ddd, 1H, J1H = 7.5,
(3C, JSn–C = 57), 29.3 (3C, 2JSn–C = 20), 30.7 (3C, 3JSn–C
3
3J1H = 11.9, J1H = 0.8, JSn–H = 35), 3.83-4.1 (m, 2H),
= 25), 33.9, 42.8, 44.8, 64.7, 74.1, 108.3 (2JSn–C = 39),
141.9 (3JSn–C = 57); 119Sn NMR: d = ꢀ27.9.
4
2
3
3
3
4.39 (dd, 1H, J1H = 6.1, J1H = 11.9, JSn–H = 20.4),
5.76 (dd, 1H, J1H = 6.1, J1H = 0.8, JSn–H = 18.6); 13C
3
4
4
1
NMR: d = 9.7 (3C, JSn–C = 284/297), 13.7 (3C), 20.5,
5.5.20. (2R,4R)-4-(3-Tributylstannyl-4-
trimethylsilylbut-1-en-1-yloxy)pentan-2-ol 2t
IR: m = 3368, 1645, 1465, 1376, 1245, 1115, 1085, 859,
840. Isomer 2tZ: Major diastereomer: 1H NMR:
d = ꢀ0.05 (s, 9H), 0.70–1.00 and 1.10–1.70 (2m, 37H),
22.8 (3JSn–C = 36), 23.8, 24.1 (3JSn–C = 32), 27.6 (3C,
3JSn–C = 53/56), 29.3 (3C, JSn–C = 19), 31.4 (2JSn–
2
C = 14), 33.4 (1JSn–C = 298/312), 45.3, 64.7, 74.8, 110.7
(2JSn–C = 40), 139.8 (3JSn–C = 46); 119Sn NMR: d = ꢀ25.0.

672
F. Fliegel et al. / Journal of Organometallic Chemistry 690 (2005) 659–673
3
2.01 (bd, 1H, J1H = 4.3), 2.51 (tdd, 1H, J2H = 11.5,
3
3
4.00–4.18 (m, 1H), 5.80 (dd, 1H, J1H = 19.1,
3J1H = 11.5, J1H = 0.9), 3.85-4.15 (m, 2H), 4.53 (dd,
3J1H = 7.2, JSn–H = 60/62), 5.8 (dd, 1H, J1H = 19.1,
4
3
3
3
3
3
1H, J1H = 6.1, J1H = 11.5, JSn–H = 19), 5.67 (dd, 1H,
3J1H = 6.1, 4J1H = 0.9, 4JSn–H = 22); 13C NMR:
2JSn–H = 70/73).
1
d = ꢀ1.20 (3C), 8.5 (3C, JSn–C = 276/289), 13.4 (3C),
5.6.2. Other side products
5.6.2.1. 3-Tributylstannylcrotonaldehyde 5. Isomer 5E:
1H NMR: d = 0.75–1.70 (m, 27H), 2.45 (d, 3H,
3
17.0, 20.3, 20.6, 23.6, 27.3 (3C, JSn–C = 52), 29.0 (3C,
2JSn–C = 9.5), 45.3, 64.1, 74.5, 114.3 (2JSn–C = 22),
137.9 (3JSn–C = 48); 119Sn NMR: d = ꢀ16.9.
3
3
4J1H = 1.8, JSn–H = 42/44), 6.19 (dq, 1H, J1H = 7.9,
1
Minor diastereomer: meaningful signals: H NMR:
3
3
4J3H = 1.8, JSn–H = 62), 10.04 (d, 1H, J1H = 7.9).
3
3
1
d = 4.30 (dd, 1H, J1H = 6.2, J1H = 11.5), 5.91 (dd,
1H, J1H = 6.2, J1H = 1.0).
Isomer 5Z: H NMR: d = 0.75–1.70 (m, 27H), 2.22
(d, 3H, J1H = 1), 6.69 (dq, 1H, J1H = 6.9, J3H = 1,
3JSn–H = 100), 9.48 (d, 1H, J1H = 6.9).
3
4
4
3
4
Isomer 2tE: meaningful signals:1H NMR: d = 5.0
(dd, 1H, J1H = 10.9, J1H = 12.2), 5.88 (dd, 1H,
3
3
3
4
1
5.6.2.2. 4-Tributylstannylpent-2-ene 6o. Isomer 6oZ: H
3J1H = 12.2, J1H = 0.5); 13C NMR: d = 44.6, 64.3,
73.6, 113.5, 139.7. 119Sn NMR: Isomer 2tE and minor
diastereomer 2tZ: d = ꢀ15.6 and -18.1.
NMR: d = 0.70–2.20 (m, 34H), 5.08 (m, 1H,
3
4
3J1H = 11.3, J3H = 6.6, J1H = 1.0), 5.41 (m, 1H,
3J1H = 11.3, J1H = 10.3, J3H = 1.6).
Isomer 6oE: H NMR: meaningful signals: d = 5.63
(m, 1H, J1H = 7.6, J1H = 15.1, J3H = 1.5).
3
4
1
5.6. Meaningful signals for SN2 substitution products
and side products
3
3
4
5.6.2.3. (Z)-7-Tributylstannylundec-5-ene 6p. 1H NMR:
d = 0.70–1.70 (m, 43H), 1.80–2.10 (m, 2H), 2.20-2.50 (m,
1H), 5.04 (dt, 1H, 3J1H = 10.8, 3J2H = 7.0), 5.32 (ddt, 1H,
3J1H = 10.8, 3J1H = 11.7, 4J2H = 1.5).
5.6.1. SN2 products
5.6.1.1. (E)-1-Tributylstannyl-3-ethoxybut-1-ene 3a.
Meaningful signals in the 1H NMR spectrum:
3
3
d = 5.49 (dd, 1H, J1H = 19.0, J1H = 5.6), 5.80 (d,
1H, J1H = 19.0).
3
5.6.2.4. (E)-1-Tributylstannyl-3-methylbut-1-ene 7o.
1H NMR: d = 0.70-1.70 (2m, 34H), 5.77 (dd, 1H,
5.6.1.2. (Z)-1-Tributylstannyl-3-ethoxypent-1-ene 3b.
1
3
3
3J1H = 5.0, J1H = 18.9), 5.92 (d, 1H, J1H = 18.9).
Meaningful signals in the H NMR spectrum: d = 5.95
(d, 1H, J1H = 13), 6.3 (dd, 1H, J1H = 8, J1H = 13).
3
3
3
5.6.1.3. (Z)-1-Tributylstannyl-3-ethoxy-4-methylpent-1-
1
ene 3d. Meaningful signals in the H NMR spectrum:
d = 6.0 (d, 1H, J1H = 12), 6.28 (dd, 1H, J1H = 8,
3J1H = 12).
Acknowledgements
3
3
The authors are grateful to Chemetall GmbH,
Crompton GmbH and Rhodia-Silicones Companies
for the gift of organometallic starting materials, to
5.6.1.4. (Z)-3-(1-Tributylstannyl-4-methylpent-1-en-3-
1
yloxy)propanol 3k. Meaningful signals in the H NMR
´ ´
CNRS, to MESR and to the ‘‘Conseil General de Loire
Atlantique’’ for financial support (S.W.B. and F.F.).
3
3
spectrum: d = 3.18 (dd, 1H, J1H = 5, J1H = 9), 6.13
(d, 1H, J1H = 13), 6.37 (dd, 1H, J1H = 9, J1H = 13).
3
3
3
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