Stereocomplementary syntheses of 1,ω-distannylated E,Z-isomeric conjugated trienes, tetraenes, and pentaenes

Article abstract of DOI:10.1002/chem.201001629

Stereoselective syntheses of 1,6-bis(tributylstannyl)hexa-1,3,5-trienes, 1,8-bis(tributylstannyl)octa-1,3,5,7-tetraenes, and 1,10-bis(tributylstannyl) deca-1,3,5,7,9-pentaenes with various methylation patterns were achieved based on stereocomplementary C=C bond-forming reactions. All-E isomers resulted from Ramberg-Baecklund rearrangements of distannylated diallyl-, allylpentadienyl-, or bis- (pentadienyl)sulfones. Mono-Z-configured 1,ω-bis(tributylstannyl)-1,3,5-polyenes emerged from (Sylvestre-)Julia olefinations of Bu₃Sn-substituted enals or dienals with Bu ₃Sn-substituted allyl or pentadienyl benzothiazolylsulfones. Related Ramberg-Baecklund approaches provided all-E-1-bromo-6-(tributylstannyl)hexa- 1,3,5-triene but not all-E-1-(tetramethyldioxaborolanyl)-6-(tributylstannyl) hexa-1,3,5-triene. Copyright

Full text of DOI:10.1002/chem.201001629

FULL PAPER
DOI: 10.1002/chem.201001629
Stereocomplementary Syntheses of 1,w-Distannylated E,Z-Isomeric
Conjugated Trienes, Tetraenes, and Pentaenes
[
a]
[b]
[c]
Jochen Burghart, Achim Sorg, and Reinhard Brꢀckner*
Abstract: Stereoselective syntheses of
,6-bis(tributylstannyl)hexa-1,3,5-tri-
enes, 1,8-bis(tributylstannyl)octa-
,3,5,7-tetraenes, and 1,10-bis(tributyl-
stannyl)deca-1,3,5,7,9-pentaenes with
various methylation patterns were
achieved based on stereocomplemen-
tary C=C bond-forming reactions. All-
E isomers resulted from Ramberg–
Bꢀcklund rearrangements of distanny-
lated di
A
H
U
G
R
N
U
G
or dienals with Bu Sn-substituted allyl
or pentadienyl benzothiazolylsulfones.
3
1
(pentadienyl)sulfones. Mono-Z-config-
ured 1,w-bis(tributylstannyl)-1,3,5-poly-
enes emerged from (Sylvestre–)Julia
Related
proaches provided all-E-1-bromo-6-
(tributylstannyl)hexa-1,3,5-triene but
not all-E-1-(tetramethyldioxaboro-
Ramberg–Bꢀcklund
ap-
1
olefinations of Bu Sn-substituted enals
lanyl)-6-(tributylstannyl)hexa-1,3,5-
triene.
Keywords: olefination · polyenes ·
rearrangement · stannanes · stereo-
selectivity
Introduction
tannylated linear conjugated polyene. In spite of this con-
ceptional advantage, such tandem Stille couplings have been
reported only occasionally, that is, for E-1,2-bis(tributylstan-
Transition-metal-catalyzed cross-coupling reactions have
revolutionized the synthesis of styrenes, stilbenes, buta-1,3-
[3,4]
nyl)ethene a few times,
methylstannyl)buta-1,3-dienes in two studies, 1,6-bis(tribu-
an isomeric mixture of 1,4-bis(tri-
[1]
[5]
dienes, and through-conjugated polyenes. An important
feature of such couplings is that they do not establish stereo-
genic C=C bonds but preserve them in the way that they
were incorporated into the starting materials. This asset cir-
cumvents the need to exert stereocontrol during the C=C
bond-forming step, which is a major advantage compared to
the Wittig reaction and other C=C bond establishing strat-
egies. Another virtue of transition-metal-catalyzed cross-
coupling reactions is their tolerance toward a variety of
functional groups, which is the more true the less nucleo-
philic the organometallic component. From the latter point
of view, organotin compounds, which undergo Stille cou-
tylstannyl)hexa-1,3,5-triene (all-E-2; Scheme 1) as an inter-
[6–8]
[8]
mediate for syntheses of xerulinic acid
and xerulin, 1,6-
bis(tributylstannyl)hepta-1,3,5-triene (all-E-9; see Scheme 3)
[2]
pling, are particularly worthwhile precursors of polyunsa-
turated structures.
The convergency of Stille coupling strategies increases
when three components are involved and one is a 1,2-distan-
nylated ethene, 1,4-distannylated buta-1,3-diene, or 1,w-dis-
[
a] Dr. J. Burghart
Carbogen Amcis AG
Hauptstrasse 171, 4416 Bubendorf (Switzerland)
[
b] Dr. A. Sorg
Basic Chemicals Research
SE, GCB/S – M311, BASF AG, 67056 Ludwigshafen (Germany)
[
c] Prof. Dr. R. Brꢁckner
Institut fꢁr Organische Chemie und Biochemie
Universitꢀt Freiburg,
Albertstraße 21, 79104 Freiburg (Germany)
Fax : (+49)761-2036100
E-mail: reinhard.brueckner@organik.chemie.uni-freiburg.de
Scheme 1. Stereoselective syntheses of 1,6-bis(tributylstannyl)-1,3,5-hexa-
triene isomers all-E- and mono-Z-2. a) CBr
on Al , 20 equiv), THF, 08C for 15 min to 258C for 30 min (73%, all-
E/mono-Z=96:4 mixture);
THF, ꢀ788C!RT, overnight (66%, mono-Z/all-E=96:4 mixture).
2 2
F (4.0 equiv), KOH (30%
2
O
3
[
6,8]
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201001629.
b) 3 (1.28 equiv), 4, KHMDS (1.2 equiv),
[7,8,19]
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[9]
as an intermediate for pyrrhoxanthin, and 1,10-bis(tributyl-
stannyl)-1,3,5,7,9-decapentaene (mono-Z-32; see Scheme 11)
[10]
as an intermediate for b-carotene. The respective distan-
nanes in the cited examples linked two different electro-
[
3]
[4f,5a,6–9]
philes either intramolecularly or intermolecularly
or
[4a,b,d–f,5]
two equivalents of a single electrophile.
Of
the
1,6-dimetalated-1,3,6-hexatrienes
reported
[11]
[12]
(
Scheme 2),
functionalized to give hexatrienes
the disilylated hexatriene all-E-5
was di-
[13]
[14]
or dodecahexaenes,
Scheme 3. Stereoselective syntheses of 1,6-bis(tributylstannyl)-1,3,5-hep-
tatriene isomers all-E- and mono-Z-9. a) CBr (4.0 equiv), KOH (33%
on Al , 10.0 equiv), THF, 08C for 15 min to 258C for 30 min (80% of
the all-E/mono-Z=89:11 mixture). b) The conditions and reagents are
the same as for (a), except the solvent is CH Cl ; 82% of a 95:5 mixture
of 9 (78%, all-E/mono-Z= 95:5 mixture) and 6-(tributylstannyl)hepta-
1,3,5-triene (4%, E,E/E,Z=67:33 mixture). c) 10 (1.18 equiv), 4,
KHMDS (1.0 equiv), THF, ꢀ788C!RT, 12 h (56%, mono-Z/all-E=95:5
mixture).
Scheme 2. 1,6-Dimetalo-1,3,5-hexatrienes other than 2.
2
F
2
2
O
3
[15]
albeit not by cross-coupling. The diboronylated hexatriene
2
2
all-E-6 did not react with 5-(bromomethylene)-(5H)-furan-
2
-one in the presence of [Pd ACHTUNGTRNENUG( PPh ) ] in the only Suzuki cou-
3 4
[16]
pling that we had tried. In contrast, each of the Coleman
tin- and boron-containing hexatrienes all-E-7 and mono-Z-7
underwent successive Stille and Suzuki coupling cleanly.
[17]
[18]
We are unaware of the existence of vinylogues reagents, that
is, any 1,8-dimetalo-1,3,5,7-tetraenes or 1,10-dimetalo-
1,3,5,7,9-pentaenes.
Results and Discussion
The scarcity of 1,w-dimetalated polyenes in general and the
[7,8,19]
success of previous syntheses
of 1,w-distannylated poly-
enes specifically caused us to broaden our engagement in
this area. As a result, we present a set of hitherto unknown
all-E- or mono-Z-configured 1,6-bis(tributylstannyl)hexa-
1,3,5-trienes,
1,6-bis(tributylstannyl)octa-1,3,5,7-tetraenes,
and 1,10-bis(tributylstannyl)deca-1,3,5,7,9-pentaene. Our
access routes are based on pertinent experience in this par-
[
6–8,19–21]
ticular class of compound
tarity of two key C=C bond-forming reactions: 1) the Ram-
with the stereocomplemen-
[22]
berg–Bꢀcklund olefination
C =C bonds of trienes and tetraenes and the C =C bond of
pentaenes and 2) the (Sylvestre–)Julia olefination
to E-selectively generate the
3
4
5
6
[23]
to es-
tablish the same bonds with a Z configuration.
By applying a protocol to make tin-free conjugated tri-
enes in one-pot sulfone bromination/Ramberg–Bꢀcklund re-
[24]
[9]
Scheme 4. Stereoselective syntheses of 1,6-bis(tributylstannyl)-1,3,5-hexa-
actions,
we treated the distannylated diallylsulfone 8
Scheme 3) and the similar compounds 11, 14, and 17
Schemes 4–6, respectively) with CBr F and KOH on
triene isomers all-E- and mono-Z-12. a) CBr
2 2
F (4.0 equiv), KOH (33%
(
(
on Al , 10.0 equiv), THF, 08C for 15 min, RT for 30 min (55%, all-E/
2
O
3
2
2
mono-Z=100:0 mixture). b) 3 (1.2 equiv), 13, KHMDS (1.2 equiv), THF,
ꢀ788C!RT, 12 h (53%, mono-Z/all-E=82:18 mixture).
[25]
Al O3
between 08C and room temperature. Purification
2
6470
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Chem. Eur. J. 2011, 17, 6469 – 6483

1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
[26]
by flash chromatography on silica gel provided the distan-
[9]
nylated trienes 9 (80–82%), 12 (55%), 15 (80–82%), and
8 (75–77% yield; Schemes 3–6, respectively). These com-
1
pounds were obtained as 87:13–100:0 mixtures of the all-E
and mono-Z isomers. The preponderance of the former
could be increased to 94:6–100:0 by conducting the Ram-
[24]
2
berg–Bꢀcklund reaction in CH Cl
rather than in THF. A
2
drawback of employing CH Cl was that up to 5% proto-
2
2
A
H
U
G
R
N
U
G
3
of the desired product.
The same one-pot sulfone bromination/Ramberg–Bꢀck-
lund olefination procedure allowed the convertion of allyl
pentadienylsulfones 19 (Scheme 7), 22 (Scheme 8), and 25
Scheme 5. Stereoselective syntheses of 2,7-bis(tributylstannyl)-2,4,6-octa-
triene isomers all-E- and mono-Z-15. a) CBr (4.0 equiv), KOH (30%
on Al , 4.0 equiv), THF, 08C for 15 min, RT for 30 min (82%, all-E/
mono-Z=89:11 mixture). b) The same conditions and reagents as in (a)
but with KOH (33% on Al , 10.0 equiv) in CH Cl (80%, all-E/mono-
Z=94:6 mixture). c) 10, 16 (1.08 equiv), KHMDS (1.02 equiv), THF,
788C!RT, 12 h (64%, mono-Z/all-E=95:5 mixture).
2
F
2
2
O
3
2
O
3
2
2
ꢀ
Scheme 7. Stereoselective syntheses of 1,8-bis(tributylstannyl)-1,3,5,7-oc-
tatetraene isomers all-E- and mono-Z-20. a) CBr
2 2
F (4.0 equiv), KOH
(
33% on Al , 10 equiv), THF, 08C for 15 min, RT for 30 min (52%,
2 3
O
all-E/mono-Z=95:5 mixture). b) 21 (1.2 equiv), 4, KHMDS (1.0 equiv),
THF, ꢀ788C!RT, 12 h (73%, mono-Z/all-E=95:5 mixture).
(
9
Scheme 9) into 1,8-distannylated tetraenes 20 (52%, E/Z=
5:5), 23 (69-79%, E/Z=79:21–83:11), and 26 (73–76%, E/
Z=80:20), respectively. Again, E-selectivity was increased
by employing CH Cl as the solvent rather than THF.
2
2
Before we became aware of the effect of CH Cl increas-
2
2
ing the selectivity, the previously used bromination/elimina-
tion procedure in THF proved suitable for transforming the
distannylated bis(pentadienyl)sulfone 28 into an all-E/
mono-Z mixture (92:8) of the linear distannylated pentaene
Scheme 6. The approach toward 2,7-bis(tributylstannyl)-1,3,5-heptatrienes
all-E- (successful) and mono-Z-18 (failed). a) CBr (4.0 equiv), KOH
33% on Al , 4.0 equiv), THF, 08C for 15 min, RT for 30 min (75%,
all-E/mono-Z=87:13 mixture). b) The same conditions and reagents as
a) but with KOH (33% on Al , 10.0 equiv) in CH Cl [82%, 93.5:6.5
2
9 (45%; Scheme 10) and the analogous sulfone 31 into an
2
F
2
(
2
O
3
all-E/mono-Z mixture (84:16) of the branched distannylated
pentaene 32 (71%; Scheme 11).
(
2
O
3
2
2
The newly prepared mono-Z-configured 1,6-distannylated
triene 9 and its congeners 12 and 15 (Schemes 3–5, respec-
of 18 (77%, all-E/mono-Z=95:5 mixture) and 2-methyl-6-(tributylstan-
nyl)hepta-1,3,5-triene (5%; isomeric composition unknown)]. c) 10
[19]
tively) were obtained in the same manner as described for
(
1.2 equiv), 13, KHMDS (1.0 equiv), THF, ꢀ788C!RT, 12 h (purification
not possible as a result of decomposition on silica gel and on Al ).
2
O
3
core structure 2 (Scheme 1), that is, by using (Sylvestre–)
Chem. Eur. J. 2011, 17, 6469 – 6483
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6471

R. Brꢁckner et al.
Scheme 8. Stereoselective syntheses of 2,9-bis(tributylstannyl)-2,4,6,8-dec-
atetraene isomers all-E- and mono-Z-23. a) CBr (4.0 equiv), KOH
33% on Al , 10 equiv), THF, 08C for 15 min, RT for 30 min (69%,
all-E/mono-Z=79:21 mixture). b) The same conditions and reagents as
in (a) but in CH Cl (79%, mono-Z/all-E=83:17 mixture). c) 10
Scheme 10. Stereoselective syntheses of 1,10-bis(tributylstannyl)-1,3,5,7,9-
2
F
2
decapentaene isomers all-E- and mono-Z-29. a) CBr F (4.0 equiv), KOH
2
2
(
2 3
O
(
2 3
33% on Al O , 10 equiv), THF, 08C for 15 min, RT for 30 min (45%,
all-E/mono-Z=92:8 mixture). b) 10 (1.2 equiv), 30, KHMDS
(1.05 equiv), THF, ꢀ788C!RT, 12 h (49%, mono-Z/all-E=95:5 mix-
ture).
2
2
(
1.28 equiv), 24, KHMDS (1.28 equiv), THF, ꢀ788C!RT, 12 h (64%,
mono-Z/all-E=95:5 mixture).
Scheme 11. Stereoselective syntheses of 1,10-bis(tributylstannyl)-1,3,5,7,9-
Scheme 9. Stereoselective syntheses of 1,8-bis(tributylstannyl)-1,3,5,7-
decapentaene isomers all-E- and mono-Z-32. a) CBr
(30% on Al , 10.0 equiv), THF, 08C for 15 min, 258C for 30 min
(71%, all-E/mono-Z=84:16 mixture). b) 33 (1.3 equiv), NaHMDS
2 2
F (4.0 equiv), KOH
nonatetraene isomers all-E- and mono-Z-26. a) CBr
33% on Al , 10 equiv), THF, 08C for 15 min, RT for 30 min (73%,
all-E/mono-Z=80:20 mixture). b) The same conditions and reagents as
in (a) but with KOH (33% on Al , 10 equiv) in CH Cl (76%, all-E/
mono-Z=80:20 mixture). c) 10 (1.3 equiv), 27 (1.0 equiv), KHMDS
1.28 equiv), THF, ꢀ788C!RT, 12 h (73%, mono-Z/all-E=95:5 mix-
ture).
2
F
2
(4.0 equiv), KOH
2 3
O
(
2 3
O
[10]
(1.2 equiv), THF, ꢀ788C, 45 min; 27, THF, ꢀ788C!258C, 12 h (83%,
“high stereoselectivity” (assignment modified in accordance with refs [19
and 20]). c) 33 (1.12 equiv), 27, KHMDS (1.12 equiv), THF, ꢀ788C!RT,
2
O
3
2
2
[
19]
(
2 h
(63%, mono-Z/all-E=94:6 mixture).
6472
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1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
3
4
Julia olefinations of appropriately stannylated/methylated
a,b-unsaturated aldehydes with appropriately stannylated/
methylated allyl(benzothiazolyl)sulfones and potassium
Table 1. Vicinal H,H coupling constants across the newly formed C =C
5
6
or C =C bonds of 1,w-bis(tributylstannyl)polyenes (trienes and tetraene
3 in CDCl and tetraenes 20 and 26 and pentaenes in [D ]benzene).
3 6
[
a]
2
Polyene
all-E isomer
mono-Z isomer
hexa
Distannanes 9 (56%, 95:5 mixture of the desired mono-Z
and undesired all-E isomers), 12 (53%; 82:18 mixture), and
ACHTUNGTRENNUNGm ethyldisilazide (KHMDS) under Barbier conditions.
J
3-H,4-H [Hz]
ACHTUNGTRENNUNG
[
6,8]
[8]
2
9
15.1
14.7
10.1
10.8
1
5 [64% (prone to decomposition on silica gel or Al O ),
2 3
12
15
18
ꢂ15
11.3
11.5
95:5 mixture] were obtained as expected.
14.7
15.2
The related 1,6-distannylated triene mono-Z-18 was inac-
unknown due to signal
overlap by the major isomer
11.1
cessible by attempted (Sylvestre–)Julia syntheses either
from aldehyde 13 and sulfone 10 (Scheme 6) or from alde-
hyde 16 and the matching sulfone 65 (formula in Table 5), at
2
2
2
0
3
6
unknown due to
higher-order splitting
unknown due to
10.9
11.3
–
1
least as a pure compound. Nonetheless the H NMR spectra
higher-order splitting
14.3
of the respective crude products exhibited resonances that
were surmised to belong to mono-Z-18; in this case, they
would have accounted for about half of the material.
J
5-H,6-H [Hz]
2
3
9
2
–
14.4
[19]
[19]
11.2
By contemplating (Sylvestre–)Julia syntheses of the 1,w-
distannylated tetraenes mono-Z-20, mono-Z-23, and mono-
Z-26 (Schemes 7–9, respectively), we had to join a reagent
that contributes one C=C bond with a reagent that contrib-
utes two. For a given target molecule, this approach left us
to decide which moiety should be incorporated into the ben-
zothiazolylsulfone and which into the aldehyde. Neverthe-
less, we never studied both possibilities because our initial
choices were satisfactory. In contrast, the C=C bonds, which
had to be established Z-selectively in the teminating step of
the (Sylvestre–)Julia syntheses of distannylated pentaenes
mono-Z-29 and mono-Z-32 (Schemes 10 and 11, respective-
ly) are symmetrically substituted. Thus, their benzothiazolyl-
sulfone and the aldehyde precursors were chosen such that
each of them contributes two C=C bonds to the target. The
yields and corresponding Z/E ratios for the distannylated
tetraenes were 73% and Z/E=95:5 for 20, 64% and Z/E=
[
a] The positional numbers of this compilation were chosen for ease of
comparison; they may differ from the IUPAC numbering in the Experi-
mental Section.
all-E-29 and mono-Z-29 did not reveal signal splitting due
to the J5H,6H coupling because of their symmetry. According-
ly, the configurational assignment is solely based on analogy
for these compounds.
Synthesis of tin-containing alcohols: The building blocks for
the Ramberg–Bꢀcklund rearrangements (i.e., allyl and pen-
tadienyl thioacetates and bromides) and Sylvestre–Julia ole-
finations (i.e., conjugated aldehydes and allyl or pentadie-
nylsulfones) were uniformly traced back to tributylstannylat-
ed allyl or pentadienyl alcohols (Scheme 12).
single exception of alcohol 37, the latter originated from the
trans-selective tributylstannylcupration
terminal (i.e., 34, 47, and 49) or an internal CꢁC bond
(i.e., 40, 43, and 45). These stannylcuprations were efficient
(71–86% yield) and regioselective, except when starting
from alkyne 43, which delivered a separable 95:5 mixture of
desired compound 42 and its regioisomer. No need for such
a separation arose when 42 was prepared by the reduction
of stannylated ester 41, which stemmed from the regioselec-
tive stannylcupration of methyl tetrolate (40) and a subse-
[28–37]
With the
[38]
of alkynes with a
[39]
[40]
9
5:5 for 23, and 73% and Z/E=95:5 for 26 (Schemes 7–9,
respectively). The yields and Z/E ratios for our access to di-
stannylated pentaene 29 were 49% and Z/E=95:5 and to
distannylated dimethylpentaene 32 were 63% and Z/E=
4:6 (Scheme 10 and 11, respectively).
ACHTUNGTRENNUNG
9
3
4
5
6
The configurations of the C =C (or C =C ) bonds, which
were created in the syntheses of the distannylated trienes
and tetraenes (or pentaenes) were deduced from the magni-
tude of the corresponding three-bond coupling constants
J3H,4H and J5H,6H, respectively (Table 1). For polyenes 9, 12,
all-E-18, mono-Z-20, mono-Z-23, and 26, which are unsym-
metrical, these coupling constants emerged from first-order
analyses of the hyperfine structure of the respective
quent
(DIBAH).
reduction
with
diisobutylaluminum
hydride
The attempted tributylstannylcupration of propargyl alco-
hol (34) followed by cuprate alkylation with MeI did not de-
liver stannylated alcohol 37 directly. Therefore, we gained
37 from 34 in a multistep sequence, that is, by using a
[ZrCp Cl ]-catalyzed (Cp=cyclopentadienyl) carboalumina-
tion followed by iodinolysis, tert-butyldimethylsilylation,
iodine/lithium exchange with tBuLi followed by quenching
with Bu SnCl, and desilylation.
3
1
[8]
H NMR peaks. For polyenes 2, 15, and 32, which are sym-
metrical, the J3H,4H and J values were determined by the
5H,6H
27]
2
2
[
[29]
[30]
SELINCOR pulse sequence and/or extracted from edited
HSQC spectra (“ H-coupled short-range H,C-COSY spec-
1
[30]
[30]
tra”).
In the unsymmetrical tetraenes all-E-20 and all-E-23, at
least one of the protons that couple across the newly formed
C=C bond was part of a higher-order subspectrum, thus hin-
dering us from extracting the J3H,4H values to prove the con-
figuration from the SELINCOR or edited HSQC spectra.
Synthesis of the Ramberg–Bꢁcklund sulfones: The stanny-
lated alcohols 35, 42, and 50 were converted into the corre-
sponding bromides 51–53 by Appel reactions with tetrabro-
momethane and triphenylphosphane (Table 2). After purifi-
1
[26]
Furthermore, the standard H NMR spectrum of pentaenes
cation by flash chromatography on silica gel, these com-
Chem. Eur. J. 2011, 17, 6469 – 6483
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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6473

R. Brꢁckner et al.
[
a]
Table 2. Syntheses of the bromide and thioacetate precursors of the sul-
fides and sulfones shown in Tables 3 and 4.
Alcohol Bromide Yield [%] Thioacetate Yield [%]
[
9]
8
8;
[
b]
3
5
51
refs [6,8]: 54
89
8
2
(
not
3
4
7
2
searched
after)
55
56
82
85
74
[
9]
52
74
(
not
4
5
6
0
searched
after)
57
58
[
41]
53
70
73
[
a] Reagents and conditions: a) CBr
CH Cl 08C, 3 h; b) HSAc (1.5 equiv), PPh
1.5 equiv), THF, 258C, 12 h. [b] This compound is shown for coherence;
4
(1.2 equiv), PPh
3
(1.2 equiv),
2
2
,
3
(1.5 equiv), DIAD
(
it was needed for the synthesis shown in Scheme 13. DIAD=diisopropyl
azodicarboxylate.
products. However, the respective bromides were prone to
isomerization and protodestannylation during purification
by flash chromatography, no matter whether silica gel or
alumina was the adsorbent. Still, the bromide derived from
alcohol 48 could be used without isolation to make sulfones
3
1 and 25 (Tables 3 and 4, respectively).
[
a]
Scheme 12. Synthesis of Sn-containing allyl and pentadienyl alcohols.
Table 3. Syntheses of the symmetric Ramberg–Bꢀcklund sulfones.
a) CuCN (1.2 equiv), nBuLi (2.4 equiv), THF, ꢀ78!25!ꢀ788C,
[
9]
HSnBu
3
(2.4 equiv), no addition of MeOH, 34, ꢀ308C, 12 h [84%;
ref. [28]: 52% (as 65% of a mixture isolated in 80% yield)]. b) Me
3
Al
, 0!258C, 12 h; ꢀ308C, I
O (1.5 equiv), 30 min (53%; ref. [29]: 60%). c) TBSCl
(2.0 equiv), DMAP (2 mol%), CH Cl
, 0!258C, 12 h
(
(
(
3.0 equiv), [ZrCp
1.5 equiv) in Et
1.1 equiv), NEt
2
Cl
2
] (0.25 equiv), 34, CH
2
Cl
2
2
Bromide
Sulfide Yield [%] Sulfone Yield [%]
2
3
2
2
5
5
2
59
91
14
28
87
19
(
85%; ref. [30]: 97%). d) 38, tBuLi (2.0 equiv), THF, ꢀ788C, 30 min;
+ ꢀ
3 4
Bu SnCl (1.05 equiv), 258C, 30 min (67%; (ref. [30]: 77%). e) Bu N F
3 (gener-
(
1.0 equiv), THF, 08C, 1 h (75%, (ref. [30]: 92%). f) CuCN (1.3 equiv),
(2.6 equiv), MeOH
1.5 equiv), 40, 1 h (82%; ref. [31]: 100%). g) DIBAH (2.3 equiv),
ated
from alcohol
5
[
c]
[
b]
nBuLi (2.6 equiv), THF, ꢀ78!25!ꢀ788C, HSnBu
3
[
9]
(
0 in situ)
[
9]
CH
2
Cl
2
, ꢀ788C, 2 h (99%; ref. [32]: 98%). h) MnO
2
(10.0 equiv), tri-
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
ethylphosphonoacetate (1.2 equiv), LiOH (2.0 equiv), THF, reflux, 2 days
53%; ref. [33]: 72%). i) CuCN (1.3 equiv), nBuLi (2.6 equiv), THF,
78!25!ꢀ788C, Bu SnH (2.6 equiv), MeOH (1.5 equiv), 43, 1 h (79%
after separation from a 95:5 mixture with the regioisomer (ref. [28]: 71%;
(
generated
from alcohol [b]
8 in situ)
(
ꢀ
[d]
31
16
3
4
+
ꢀ
[
35]
[a] Reagents and conditions: a) Na S·9H O (1.00 equiv), NH HSO4
ref. [34]: 82%). j) DIBAH (2.3 equiv), CH
k) CuCN (1.3 equiv), nBuLi (2.6 equiv), THF, ꢀ78!25! ꢀ788C,
HSnBu
(2.6 equiv), no addition of MeOH, 45, ꢀ308C, 12 h (71%;
ref. [36]: 87%). l) CuCN (1.5 equiv), nBuLi (3.0 equiv), THF, ꢀ78!25!
788C, HSnBu
(3.0 equiv), no addition of MeOH, 47, ꢀ308C, 12 h
86%; ref. [28]: 92%). m) CuCN (1.05 equiv), nBuLi (2.0 equiv), THF,
2
Cl
2
, ꢀ788C, 2 h (86%).
2
2
4
(
(
1 mol%), THF, H
2
2 2 7 4 6 24
O, 25 8C, 24 h; b) H O (5–9 equiv), [Mo ACHTUNGTRENNUNG( NH ) O ]
0.20 equiv), EtOH, 08C, 2 h. [b] Partial decomposition during column
. [c] Yield over the three
3
2 3
chromatography either on silica gel or Al O
steps from alcohol 50. [d] Yield over the three steps from alcohol 48.
ꢀ
3
(
ꢀ
78!25!ꢀ788C, HSnBu
308C, 12 h (77%; ref. [37]: 78%). Cp=cyclopentadienyl, DIBAH=di-
hydride, DMAP=4-(dimethylamino)pyridine,
3
(2.0 equiv), no addition of MeOH, 49,
ꢀ
Under Mitsunobu conditions [i.e., diisopropyl azodicar-
boxylate (DIAD), triphenylphosphane, and thioacetic acid],
stannylated alcohols 35, 37, 42, 46, and 50 furnished the cor-
responding thioacetates 54–58 in 73–89% yield (Table 2).
They could be purified without interfering isomerization re-
actions.
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
isobutylaluminium
TBSCl=tert-butyldimethylsilyl chloride.
pounds were obtained in 70–88% yield. Stannylated alco-
hols 37, 46, and 48 seemed to react analogously, as indicated
by H NMR spectroscopic analyses of the respective crude
Bisstannylated symmetric sulfones 14, 28, and 31 were ob-
tained after combining two equivalents of the respective
1
6474
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ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 6469 – 6483

1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
[
a]
Table 4. Syntheses of the unsymmetric Ramberg–Bꢀcklund sulfones.
phosphane, and benzothiazolthiol (84–98% yield). Subse-
quent oxidation reactions with peroxomolybdate(VI) re-
generated in situ furnished the mentioned sulfones in 63–
[43]
9
0% yield.
Thioacetate Bromide
Sulfone Yield [%]
Finally, the alcohols shown in Table 5 were oxidized with
MnO , thus providing the stannylated aldehydes depicted
therein in 73–88% yield.
2
[
9]
[b]
56
55
55
58
57
51
51
52
51
52
8
62
41
48
59
57
11
17
19
22
Conclusion and Perspectives
[
[
[
c]
c]
c]
We have synthesized a family of 1,w-bis(tributylstannylated)
conjugated trienes, tetraenes, and pentaenes stereoselec-
tively. Their central C=C bond was established by Ram-
berg–Bꢀcklund rearrangements in THF with moderate-to-
good E selectivities or by (Sylvestre–)Julia olefinations with
very good Z selectivities (usually Z/Eꢃ95:5). The E selec-
(from al-
cohol
[
d]
5
6
25
36
tivities were improved by up to 6% in CH Cl versus THF,
4
8 in
2
2
situ)
albeit at the cost of up to 5% protonolysis of the less-hin-
2
dered C
A
H
U
G
R
N
N
(sp )ꢀSnBu bond. Linear polyenes formed most se-
[
a] Reagents and conditions: a) thioacetate (1.10 equiv), KOH (4.0 equiv),
MeOH, 08C, 10 min; bromide (1.00 equiv), 2 h, 258C; isolation of crude prod- lectively, for example, with E/Z=96:4 in the case of hexa-
uct. b) H (5–9 equiv), [Mo (NH
3
2
O
2
7
A
T
G
R
N
N
4
)
6
O
24
]
(0.20 equiv), EtOH, 08C, 2 h. triene 32.
[
9]
[
7
b] Yield of 56+51!sulfide: 87%; yield of oxidation sulfide!sulfone:
The 1,6-distannylated trienes, 1,8-distannylated tetraenes,
and 1,10-distannylated pentaenes, which became accessible
through using the mentioned key reactions, merit interest as
bifunctional reagents for three-component Stille coupling
reactions. Such a usage had already been demonstrated for
[
9]
1%. [c] Partial decomposition during column chromatography either on
. [d] Yield over the three steps from alcohol 48.
2 3
silica gel or Al O
bromide with one equivalent of Na S in S 2 reactions cata-
lyzed by 1 mol% Bu N HSO (Table 3).
sulfides were oxidized after isolation (i.e., 59) or as crude
products by employing hydrogen peroxide and peroxomo-
lybdate catalysis,
Bꢀcklund sulfones that were isomerically pure albeit in
widely differing yields (16–88%).
2
N
[42]
+
ꢀ
[6,7,8]
[46]
[9]
The resulting
trienes all-E-2,
mono-Z-2, and all-E-9 and for pen-
4
4
[10]
taene all-E-32. By taking into account the variability of
the methylation pattern with which we actually could endow
or with which one should be able to endow this class of re-
agent, a manifold of applications in the stereoselective syn-
thesis of extended polyenes is conceivable. In this regard, it
is noteworthy that the side chains of hexatriene all-E-18 on
the one hand and hexatriene all-E-15, tetraene all-E-26, and
[43]
thus providing the desired Ramberg–
Table 4 shows that we made bisstannylated unsymmetric
[9]
sulfones 8, 11, 17, 19, and 25 accessible from thioacetates
5–58 in 36–62% overall yields
5
by KOH-mediated methanoly-
sis, alkylation of the resulting
thiolate in situ with the appro-
priate allyl or pentadienyl bro-
[
a]
Table 5. Synthesis of the (Sylvestre–)Julia olefination substrates.
VI
mide, and Mo -catalyzed oxi-
dation with hydrogen perox-
ide.
[
43]
Alcohol Sulfide Yield [%]
Sulfone Yield [%]
Aldehyde Yield [%]
[
8]
[8]
3
5
60
61
96
3
83
65
4
88; ref. [32]: 98
Synthesis of (Sylvestre–)Julia
aldehydes and sulfones: The
preparation of stannylated allyl
or pentadienyl benzothiazolyl-
sulfones for (Sylvestre–)Julia
olefinations relied on a previ-
[
b]
[c]
37
ꢄ84
65
13
84
[
19]
[19]
4
4
2
6
62
98
10
90
16
24
87; ref. [32]: 100
not searched after
not searched after
73
[19]
ously
used
methology
[19]
9
5;
68; ref. [19]: 48;
ref. [10]: 61
[
44]
4
5
8
0
63
64
33
21
27
34
78; ref. [45]: 96
86; ref. [45]: 70
(
Table 5). Five of the alcohols
ref. [10]: 93
were converted into stannylated
allyl or pentadienyl benzothia-
zolyl sulfides 60–64 by using
Mukaiyama redox condensation
95
63
[
a] Reagents and conditions: a) benzo-1,3-thiazol-2-thiol (1.05 equiv), PPh
THF, 08C, 1–2 h. b) H (10.0 equiv), [Mo (NH
(0.2 equiv), EtOH, 08C!RT, 2 h. c) MnO
20.0 equiv), CH Cl , RT, 4–12 h. [b] This compound contained a contaminant, which was not identified.
3
(1.10 equiv), DIAD (1.09 equiv),
2
O
2
7
A
H
U
T
E
N
N
4
)
6
O
24
]
2
(
2
2
reactions with DIAD, triphenyl- [c] This compound is mentioned in the discussion of Scheme 6, but is not depicted elsewhere.
Chem. Eur. J. 2011, 17, 6469 – 6483
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6475

R. Brꢁckner et al.
pentaene all-E-32 on the other hand are interspersed exactly
as widely as in head-to-tail and head-to-head linked iso-
prene units, respectively. This property makes compound 18
a potential building block for retinoids and compounds 18,
obtained the B/Sn-containing diallyl sulfide 70 (Scheme 13).
Oxidation to the corresponding diallylsulfone 71 succeeded
with Montmorillonite-supported oxone as an oxidant.
However, we failed to brominate and contract this material
into the desired triene all-E-7 under the previously estab-
lished conditions and a few variations thereof.
[55]
[47]
15, 26, and 32 potential building blocks for carotenoids.
Moreover, distannylated tetraene all-E-23 displays methyl
substituents precisely at the unusual distance encountered in
Conversely, the stannylated allyl bromide 51 mentioned
above and the unprecedented bromoallyl thioacetate 72
were linked by treatment with potassium methoxide to give
Br/Sn-containing diallyl sulfide 74 (94%; Scheme 14). Oxi-
[48]
the core of the C carotenoids peridinin and pyrrhoxan-
3
7
[49]
thin, synthetic studies of which represent another focus of
research in our group.
[9,50]
Last but not least, we tested the scope and limitations of
our Ramberg–Bꢀcklund route to all-E-configured 1,w-dime-
talopolyenes also with the goal of making the Coleman 1-
[
18]
(
pinacolboryl)-6-(tributylstannyl)hexatriene all-E-7
and
the hitherto unknown 1-bromo-6-(tributylstannyl)hexatriene
all-E-76 (Schemes 13 and 14, respectively). By relying on
Scheme 14. Synthesis of a tin- and bromine-containing triene. a) KOH
(
(
(
(
5.0 equiv) in MeOH, 72 (1.1 equiv), 08C, 5 min; 51 (1.0 equiv), 1 h
91%). b) AcSH (1.14 equiv), PPh (1.2 equiv), diethyl azodicarboxylate
1.2 equiv), THF, 08C, 1 h (94%). c) H (9.0 equiv), [Mo (NH
0.20 equiv), EtOH, 08C, 1 h (91%). d) CBr (5.0 equiv), KOH (33%
, 10.0 equiv), THF, 08C!RT, 30 min (61%, all-E-76/mono-Z-
6=88:12 mixture).
3
2
O
2
7
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
4 6 24
) O ]
2
F
2
2 3
on Al O
7
dation to the corresponding diallylsulfone 75 was effected
VI
[43]
by hydrogen peroxide with Mo catalysis (91%). Under
the previously established Ramberg–Bꢀcklund conditions,
this compound rendered 61% of 1-bromo-6-(tributylstan-
nyl)hexatriene all-E-76 as an 88:12 mixture of all-E and
mono-Z isomers. Whether this compound undergoes a Stille
coupling reaction with anything other than itself needs to be
studied. Our “amphiphilic” triene all-E-76 has an analogous
design to triene all-E-77, which underwent a Suzuki cross-
coupling reaction with a dienylboronic acid in instead of oli-
[
18]
Scheme 13. Attempted synthesis of the Coleman
tin- and boron-con-
Cl ] (10 mol%) and
BH (10 mol%) in the absence of light; THF, 08C, 2 h; addition to
the silyl ether (1.0 equiv), pinacolborane (1.05 equiv), NEt (10 mol%),
N F (1.0 equiv), THF, 08C!RT, 2 h (75%).
(1.2 equiv), CH Cl , 08C, 3 h (50%). d) KOH
taining triene all-E-7. a) Prereaction between [ZrCp
2
2
[
51]
LiEt
3
3
+
ꢀ
6
08C, 16 h (61%). b) Bu
4
c) CBr (1.2 equiv), PPh
4
3
2
2
(
(
(
5.0 equiv), MeOH, 08C, 2 h (89%). e) 68, THF, ꢀ788C, tBuLi
1.0 equiv), 30 min; 69 (1.0 equiv), ꢀ788C!RT (82%). f) Oxone
[
55]
5 4 2 4 2 2
KHSO ·KHSO ·2K SO ; 2.5 equiv) on Montmorillonite, CH Cl , RT,
[57]
2
h
[91% of crude product (spectroscopically essentially pure)].
g) CBr (4.0 equiv), KOH (30% on Al , 10.0 equiv), absence or pres-
gomerization through homo-coupling.
2
F
2
2 3
O
ence of pinacol (3.0 equiv), THF, 08C!RT, 30 min.
Experimental Section
the stannylated allyl thioacetate 54 mentioned above and on
[52]
2
General: The reactions were performed under N in glassware dried with
an improved access via silylether 66 (and its desilylation
a heatgun under vacuum. The products were purified by flash chromatog-
+
ꢀ
with Bu N F rather than with citric acid as previously de-
[26]
4
raphy on silica gel or deactivated alumina (filling height, column diam-
[52]
[53]
[54]
scribed) to the known borylated allyl bromide 69, we
eter, and eluent are given in parantheses; which fractions contained the
6476
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ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 6469 – 6483

1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
isolated product are indicated as “fractions xx-yy”) on Merck silica gel 60
0.040–0.063 mm). The yields refer to analytically and/or spectroscopical-
3’), 29.18 (flanked by Sn isotope satellites as an incompletely resolved d,
2
2
(
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 3 ꢃ C-2’), 29.21 (flanked by Sn isotope satel-
1
2
2
ly pure samples. H NMR spectra were obtained in CDCl
3
(dCHCl3
=
lites as an incompletely resolved d, JC-2’,117Sn ꢂ JC-2’,119Sn ꢂ19 Hz; 3 ꢃ C-2’),
7
.26 ppm) or in C (dC6D5H =7.15 ppm) on Varian Mercury VX 300,
6
D
6
126.19 (flanked by Sn isotope satellites as an incompletely resolved d,
3
3
Bruker AM 400, and Bruker DRX 500 spectrometers. The integrals
agree with the given assignments. The coupling constants are given in
J
C-4,117Sn ꢂ JC-4,119Sn ꢂ62 Hz; C-4), 134.62 (flanked by Sn isotope satellites
3
3
as an incompletely resolved d,
(flanked by Sn isotope satellites as 2 interwoven doublets,
364.3, JC-1,119Sn =381.5 Hz; C-1), 138.99 (flanked by Sn isotope satellites as
J
C-3,117Sn ꢂ JC-3,119Sn ꢂ74 Hz; C-3), 134.76
1
3
1
Hertz (Hz). C NMR spectra were obtained in CDCl
3
and C
6
D
6
(d=
J
C-1,117Sn
=
1
7
7.10 and 128.62, respectively) on Bruker AM 400 and Bruker DRX 500
1
13
2
2
spectrometers. The assignments of H and C NMR spectroscopic reso-
nances refer to the IUPAC nomenclature, except within substituents
an incompletely resolved d, JC-5,117Sn ꢂ JC-5,119Sn ꢂ30 Hz; C-5), 146.18 (C-6),
147.33 ppm (flanked by Sn isotope satellites as an incompletely resolved
2
2
(
where primed numbers are used). Heteronuclear couplings: the ratio be-
d,
J
C-2,117Sn ꢂ JC-2,119Sn ꢂ8 Hz; C-2); IR (film): n˜ =2955, 2925, 2875, 2855,
n
n
tween the coupling constants
bonds must equal the quotient of the gyromagnetic ratios of
(
J
1H,119Sn and
J
1H,117Sn across n interspersed
1465, 1420, 1375, 1340, 1290, 1250, 1180, 1150, 1070, 995, 960, 945, 875,
860, 750, 695, 660, 595 cm ; HRMS (CI, 120 eV): calcd for C27
1
19
ꢀ1
Sn
H
53Sn
2
:
7
ꢀ1 ꢀ1 [58]
117
7
ꢀ1 ꢀ1 [58]
ꢀ9.9708ꢃ10 radT
s
)
and Sn (ꢀ9.5301ꢃ10 radT
s
), that is,
617.21912 [MꢀBu]; found: 617.22020 (+1.8 ppm).
ACHTUNGTRNENUNG( 1E,3E,5E)-2-Methyl-1,6-bis(tributylstannyl)hexa-1,3,5-triene (all-E-12):
1
.046. The same is true for the ratio between the coupling constants
n
n
J
13C,119Sn and J13C,117Sn. In alkenylstannanes, the limits of the spectral resolu-
Following the general procedure, all-E-12 was prepared in THF from bi-
sallylsulfone 11 (188 mg, 0.255 mmol), CBr F (96.0 mL, 214 mg,
tion and occurrence of line splitting through H,H coupling allowed the
2
2
1
13
119
117
determination of H,Sn and C,Sn coupling constants for Sn and Sn
2 3
1.02 mmol, 4.0 equiv), and KOH on Al O (143 mg, 2.55 mmol,
separately only for large J values; small J values are usually isotope-aver-
10.0 equiv). After flash chromatogra-
[
59]
[26]
aged. The mass-spectrometric analysis was carried out by Dr. J. Wçrth
and C. Warth (Institut fꢁr Organische Chemie and Biochemie, Universi-
tꢀt Freiburg). Combustion analyses were carried out by E. Hickl (Institut
fꢁr Organische Chemie and Biochemie, Universitꢀt Freiburg). The IR
spectra were obtained on a Perkin–Elmer Paragon 1000 spectrometer.
phy on deactivated Al
2 3
O (5ꢃ2 cm,
cyclohexane/NEt 98:2 (v/v), fractions
3
2 and 3), all-E-12 was obtained as a
colorless oil (94.2 mg, 55%, all-E/
1
mono-Z=100:0). H NMR (400.1 MHz, CDCl
4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H ), 0.929 (t, J4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H
, 6H; 3 ꢃ 1’-H ), 1.02 (m , each peak flanked by Sn isotope satellites
as 2 interwoven doublets, J1’-H,117Sn =49.3,
), 1.37 (qt, J3’,4’ =J3’,2’ =7.3 Hz, 6H; 3 ꢃ 3’-H
.3 Hz, 6H; 3 ꢃ 3’-H ), 1.54–1.71 (m, 12H; 6 ꢃ 2’-H
Sn isotope satellites as an incompletely resolved d,
3
/CHCl
3
): d=0.926 (t,
J
3
3
), 1.01
Syntheses of all-E-polyene distannanes:
(
m
c
2
c
General procedure for Ramberg–Bꢁcklund polyene syntheses: CBr
4.0 equiv) was added to a solution (ca. 0.05m) of the bisallylsulfone in
THF or CH Cl followed by KOH (33% on Al , 10.0 equiv) as one
2 2
F
2
2
J
1’-H,119Sn =51.3 Hz, 6H; 3 ꢃ 1’-
), 1.38 (qt, J3’,4’ =J3’,2’
(
H
7
2
2
=
2
2
2 3
O
2
2
), 1.96 (s, flanked by
portion at 08C. After 15 min at 08C and 30 min at room temperature, the
mixture was diluted with pentane. Filtration through a pad of celite and
evaporation of the solvent under reduced pressure was followed by pu-
rification by chromatography on neutral alumina (deactivated by 3%
4
4
J
2-Me,117Sn ꢂ J2-Me,119Sn
ꢂ9 Hz, 3H; 2-CH
3
), 6.17 (s, flanked by Sn isotope satellites as an incom-
2
2
pletely resolved d,
J
1-H,117Sn ꢂ J1-H,119Sn ꢂ67 Hz, 1H; 1-H), 6.31 (dd, J4,3
=
1
J
5.7, J4,5 =9.8 Hz, 1H; 4-H), 6.46 (d, J3,4 =14.5 Hz, 1H; 3-H), 6.46 (d,
H
2
O).
(1E,3E,5E)-1,6-Bis(tributylstannyl)hepta-1,3,5-triene (all-E-9): By fol-
lowing the general procedure, all-E-9 was prepared in THF from bisallyl-
sulfone (368 mg, 0.498 mmol),
CBr (184 mL, 418 mg, 2.0 mmol,
.0 equiv), and KOH on Al
850 mg, 4.98 mmol, 10.0 equiv). After
6.5 =18.9 Hz, each peak flanked by Sn isotope satellites as an incom-
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
2
pletely resolved d,
J
6-H,117Sn ꢂ J6-H,119Sn ꢂ72 Hz, 1H; 6-H), 6.86 ppm (dd,
J
5.6 =18.6, J5.4 =9.8 Hz, each peak flanked by Sn isotope satellites as 2 in-
3
3
13
8
terwoven doublets, J5-H,117Sn =59.1, J5-H,119Sn =62.8 Hz; 5-H); C NMR
(100.6 MHz, CDCl /CDCl ): d=9.89 (3 ꢃ C-1’), 10.59 (3 ꢃ C-1’), 13.90
2 2
F
3
3
4
2
O
3
(3 ꢃ C-4’), 13.91 (3 ꢃ C-4’), 20.96 (flanked by Sn isotope satellites as an
3
3
(
incompletely resolved d, J2-Me,117Sn ꢂ J
2-Me,119
ꢂ33 Hz; 2-CH ), 27.69
Sn
3
3
[
26]
flash chromatography
on deactivat-
(flanked by Sn isotope satellites as an incompletely resolved d, J
C-3’,117Sn
ꢂ
3
ed Al
0:1 (v/v), fractions 3 and 4), all-E-9 was obtained as a yellowish oil
263 mg, 80%, all-E/mono-Z=89:11). By following the general proce-
dure, all-E-9 was also prepared in CH Cl from bisallylsulfone 8 (250 mg,
.338 mmol), CBr (127 mL, 283.3 mg, 1.350 mmol), and KOH on Al
190 mg, 3.98 mmol, 10.0 equiv). After flash chromatography on deacti-
vated Al (5ꢃ2 cm, cyclohexane/NEt 50:1 (v/v), fractions 3 and 4),
the product was obtained in 82% yield as an 95:5 mixture of all-E-9
177.2 mg, 78%, 95:5 all-E/mono-Z) and 6-(tributylstannyl)hepta-1,3,5-
2
O
3
(5ꢃ2 cm, cyclohexane/NEt
3
JC-3’,119Sn ꢂ52 Hz; 3 ꢃ C-3’), 27.70 (flanked by Sn isotope satellites as an
3
3
5
(
incompletely resolved d,
J
117 ꢂ J
119 ꢂ55 Hz; 3
ꢃ C-3’), 29.58
C-3’, Sn
C-3’, Sn
2
(flanked by Sn isotope satellites as an incompletely resolved d, J
C-2’,117Sn
ꢂ
2
2
2
JC-2’,119Sn ꢂ21 Hz; 3 ꢃ C-2’), 29.66 (flanked by Sn isotope satellites as an
2
2
0
(
2
F
2
2
O
3
incompletely resolved d, J
117 ꢂ J
119 ꢂ20 Hz; 3 ꢃ C-2’), 130.99 (C-
C-2’, Sn
C-2’, Sn
[
26]
4), 134.52 (C-6), 134.75 (C-1), 137.78 (C-3), 148.20 (C-5), 151.33 ppm (C-
2); IR (film): n˜ =2955, 2925, 2875, 2845, 1690, 1600, 1570, 1460, 1440,
1415, 1375, 1340, 1290, 1250, 1180, 1145, 1070, 1025, 1000, 960, 875, 810,
2
O
3
3
ꢀ
1
(
690, 675 cm ; no HRMS spectrum was obtained because the compound
did not stand up to the ionization conditions.
1
triene (5.1 mg, 4%; E,E/E,Z=67:33) as
(
(
solved d,
J
a
colorless oil. H NMR
/TMS): d=0.88 (t, J4’,3’ =7.1 Hz, 18H; 6 ꢃ 4’-H ), 0.89
c
, each peak flanked by Sn isotope satellites as an incompletely re-
499.9 MHz, CDCl
3
3
AHCTUNGTRENNUNG
m
2
2
J
1’-H,117Sn ꢂ J1’-H,119Sn ꢂ50 Hz, 12H; 6 ꢃ 1’-H
2
), 1.29 (qt, J3’,4’
=
1
2 2
F
2 2
3’,2’ =7.3 Hz, 12H; 6 ꢃ 3’-H ), 1.43–1.54 (m, 12H; 6 ꢃ 2’-H ), 2.02 (s,
O
3
2
3
flanked by Sn isotope satellites as an incompletely resolved d, J7-H,117Sn
ꢂ
3
3
[26]
J
7-H,119Sn ꢂ46 Hz, 3H; 7-H ), 6.16 (dd, J3,4 =14.5, J3,2 =10.4 Hz, 1H; 3-H),
chromatography
on deactivated
6
.22 (d, J5,4 =10.7 Hz, 1H; 5-H), 6.28 (d, J1,2 =18.6 Hz, each peak flanked
Al O (5ꢃ2.5 cm, cyclohexane/NEt3
2
3
2
2
by Sn isotope satellites as 2 interwoven doublets, J1-H,117Sn =59.9, J1-H,119Sn
60.5 Hz, 1H; 1-H), 6.55 (dd, 4.3 =14.8, 4,5 =11.0 Hz, 1H; 4-H),
.62 ppm (dd, J2,1 =18.6, J2,3 =10.1 Hz, 1H; 2-H); C NMR (125.7 MHz,
CDCl /TMS): d=9.14 (flanked by Sn isotope satellites as 2 interwoven
doublets,
100:1 (v/v), fractions 3 and 4), all-E-15
was obtained as yellowish oil
=
J
J
a
1
3
6
(174.3 mg, 82%, all-E/mono-Z=89:11). This compound was also pre-
pared in CH Cl from bisallylsulfone 14 (300 mg, 0.399 mmol), CBr F
2
3
2
2
2
1
1
J
C-1’,117Sn =315.9,
J
C-1’,119Sn =331.0 Hz; 3 ꢃ C-1’), 9.52 (flanked
2 3
(150 mL, 336 mg, 1.60 mmol, 4.0 equiv), and KOH on Al O (223 mg,
1
[26]
by Sn isotope satellites as 2 interwoven doublets,
C-1’,119Sn =343.9 Hz; 3 ꢃ C-1’), 13.89 (6 ꢃ C-4’), 20.17 (flanked by Sn iso-
tope satellites as an incompletely resolved d,
C-7), 27.18 (flanked by Sn isotope satellites as an incompletely resolved
J
C-1’,117SnJ =328.8,
3.99 mmol, 10.0 equiv). After flash chromatography
on deactivated
1
J
Al O (5ꢃ2 cm, cyclohexane/NEt 98:2 (v/v), fractions 3 and 4), all-E-15
was obtained as a yellowish oil (220 mg, 80%, all-E/mono-Z=94:6).
2
3
3
2
2
J
C-7,117Sn ꢂ JC-7,119Sn ꢂ38 Hz;
1
H NMR (499.9 MHz, C D /C D H): d=1.07 (t, J =7.2 Hz, 18H; 6 ꢃ
6
6
6
5
4’,3’
3
3
d, JC-3’,117Sn ꢂ JC-3’,119Sn ꢂ55 Hz; 3 ꢃ C-3’), 27.51 (flanked by Sn isotope sat-
3 c
4’-H ), 1.14 (m , each peak flanked by Sn isotope satellites as an incom-
3
3
2
2
ellites as an incompletely resolved d,
J
C-3’,117Sn ꢂ JC-3’,119Sn ꢂ56 Hz; 3 ꢃ C-
pletely resolved d, J1’-H,117Sn ꢂ J1’-H,119Sn ꢂ52 Hz, 12H; 6 ꢃ 1’-H
2
), 1.52 (qt,
Chem. Eur. J. 2011, 17, 6469 – 6483
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6477

R. Brꢁckner et al.
J
3’,4’ =J3’,2’ =7.4 Hz, 12H; 6 ꢃ 3’-H
2
), 1.70–1.82 (m, 12H; 6 ꢃ 2’-H
2
), 2.08
151.72 ppm (flanked by Sn isotope satellites as an incompletely resolved
2
2
(
J
s, flanked by Sn isotope satellites as an incompletely resolved d,
d, JC-2,117Sn ꢂ J
C-2,119Sn
ꢂ7 Hz; C-2); IR (film): n˜ =2960, 2925, 2870, 2850,
3
3
3
3
1-H,117Sn ꢂ J8-H,117Sn ꢂ J1-H,119Sn ꢂ J8-H,119Sn ꢂ45 Hz, 6H; 1-H
3
and 8-H
3
), 6.30
1650, 1635, 1580, 1460, 1415, 1375, 1155, 1075, 1020, 960, 875, 860, 790,
ꢀ1
(
d, J3,4 =J6,5 =10.0 Hz, 2H; 3-H and 6-H), 6.55 ppm (d, J4,3 =J5,6 =10.4 Hz,
685, 660, 590 cm ; HRMS (CI, 120 eV): calcd for C H Sn : 631.23477
2
8
55
2
1
3
+
2
H; 4-H and 5-H); C NMR (125.7 MHz, CDCl
3
/CDCl
3
): d=9.20
J =
C-1’,119Sn
[M ꢀBu]; found: 631.23340 (ꢀ2.2 ppm).
1
(
J
flanked by Sn isotope satellites as 2 interwoven doublets,
(
1E,3E,5E,7E)-1,8-Bis(tributylstannyl)octa-1,3,5,7-tetraene
(all-E-20):
1
1
1
C-1’’,119Sn =330.6 Hz; JC-1’,117Sn = JC-1’’,117Sn =315.5 Hz; 6 ꢃ C-1’), 13.70 (6 ꢃ
Following the general procedure, all-E-20 was prepared in THF from bis-
allylsulfone 19 (199 mg, 0.265 mmol), CBr (132 mL, 287 mg, 1.33 mmol,
C-4’), 20.02 (C-1, C-8), 27.38 (flanked by Sn isotope satellites as an in-
A
H
U
G
R
N
U
G
2 2
F
3
3
3
3
completely resolved d, JC-3’,117Sn ꢂ JC-3’’,117Sn ꢂ JC-3’,119Sn ꢂ JC-3’’,119Sn ꢂ55 Hz; 6
ꢃ C-3’), 29.17 (flanked by Sn isotope satellites as an incompletely re-
2
2
2
2
solved d,
J
C-2’,117Sn ꢂ JC-2’’,117Sn ꢂ JC-2’,119Sn ꢂ JC-2’’,119Sn ꢂ21 Hz;
6 ꢃ C-2’),
1
26.33 (flanked by Sn isotope satellites as an incompletely resolved d,
C-4,117Sn ꢂ JC-5,117Sn ꢂ JC-4,119Sn ꢂ JC-5,119Sn ꢂ66 Hz; C-4, C-5), 139.58 (flanked
3
3
3
3
J
2
2
by Sn isotope satellites as an incompletely resolved d, JC-3,117Sn ꢂ JC-6,117Sn
ꢂ
2
2
J
C-3,119Sn ꢂ JC-6,119Sn ꢂ30 Hz; C-3, C-6), 144.98 ppm (C-2, C-7; the E configu-
ration of the C =C double bond was shown by an edited HSQC spec-
4
5
5.0 equiv), and KOH on Al
2
O
3
(225 mg, 1.33 mmol, 5.0 equiv). After
on deactivated Al (5ꢃ2 cm, cyclohexane/
3
98:2 (v/v), fractions 3 and 4), all-E-20 was obtained as a yellowish
[
26]
1
3
flash chromatography
NEt
oil (95.1 mg, 52%, all-E/mono-Z=95:5). H NMR (499.9 MHz, C
H): d=0.93 (t, J4’,3’ =7.3 Hz, 18H; 6 ꢃ 4’-H ), 1.03 (m , each peak
2 3
O
trum (499.9/125.7 MHz, CDCl
1
1
ting due to J4,3 =J5,6 =11.2 and J4,5 =14.7 Hz); IR (film): n˜ =2955, 2925,
2
7
3
) in which the C NMR resonance d=
1
1
26.33 ppm (C-4, C-5) was split by the coupling
51.8 Hz, such that both the low- and the highfield branch revealed split-
J
C-4,4-H = JC-5,5-H
=
1
6
6
D /
C
6
D
5
3
c
2
ꢀ1
flanked by Sn isotope satellites as an incompletely resolved d, J1’-H,117Sn
ꢂ
870, 2855, 1465, 1375, 1070, 960, 940, 875, 840, 770 cm ; HRMS (EI,
2
+
J
’-H
1’-H,119Sn ꢂ53 Hz, 12H; 6 ꢃ 1’-H
2
), 1.37 (qt, J3’,4’ =J3’,2’ =7.4 Hz, 12H; 6 ꢃ
), 6.19–6.25 (m , 2H, 4-H and 5-H),
0 eV): calcd for
C
28
H55Sn
2
:
631.23477 [M ꢀBu]; found: 631.23169
3
2
), 1.52–1.69 (m, 12H; 6 ꢃ 2’-H
2
c
(
ꢀ4.9 ppm).
(1E,3E,5E)-2-Methyl-1,6-bis(tributylstannyl)hepta-1,3,5-triene (all-E-18):
Following the general procedure, all-E-18 was prepared in THF from bi-
sallylsulfone 17 (217 mg, 0.288 mmol), CBr (110 mL, 250 mg,
.15 mmol, 4.0 equiv), and KOH on
Al (490 mg, 2.88 mmol, 10.0 equiv).
After flash chromatography
activated Al (5ꢃ2 cm, cyclohexane/
NEt 98:2 (v/v), fractions 3 and 4), all-
6
.26–6.36 (m
c
, 2H, 3-H and 6-H), 6.43 (d, J1,2 =J8,7 =18.8 Hz, each peak
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
flanked by Sn isotope satellites as an incompletely resolved d, J1-H,117Sn
ꢂ
2
2
2
J
8-H,117Sn ꢂ J1-H,119Sn ꢂ J8-H,119Sn ꢂ70 Hz, 2H; 1-H and 8-H), 6.81 ppm (dd,
2
F
2
J
2,1 =J7,8 =18.7, J2,3 =J7,6 =9.8 Hz, each peak flanked by Sn isotope satel-
1
3
3
3
lites as
2
interwoven doublets,
J
2-H,117Sn = J7-H,117Sn =57.8,
2-H,119Sn
J =
2
O
3
3
13
J
6 6 6 6
7-H,119Sn =59.7 Hz, 2H; 2-H and 7-H); C NMR (125.7 MHz, C D /C D ):
[
26]
on de-
d=9.88 (flanked by Sn isotope satellites as 2 interwoven doublets,
2
O
3
1
1
J
C-1’,117Sn =328.2,
J
C-1’,119Sn =343.6 Hz; 6 ꢃ C-1’), 13.90 (6 ꢃ C-4’), 27.69
3
3
(
flanked by Sn isotope satellites as 2 interwoven doublets, JC-3’,117Sn =53.0,
C-3’,119Sn =55.1 Hz; 6 ꢃ C-3’), 29.56 (flanked by Sn isotope satellites as an
E-18 was obtained as a yellowish oil
3
J
(
148 mg, 75%, all-E/mono-Z=87:13). Following the general procedure,
2
2
incompletely resolved d,
(
ven doublets,
1
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20.6 Hz; 6 ꢃ C-2’), 132.52
all-E-18 was also prepared in CH
.266 mmol), CBr (100 mL, 222 mg, 1.06 mmol, 4.0 equiv), and KOH
on Al (150 mg, 2.66 mmol, 10.0 equiv). After flash chromatography
on deactivated Al (5ꢃ2 cm, cyclohexane/NEt 98:2 (v/v), fractions 3
2 2
Cl from bisallylsulfone 17 (200 mg,
C-4, C-5), 135.00 (C-1, C-8, flanked by Sn isotope satellites as 2 interwo-
0
2 2
F
1
1
1
1
J
C-1,117Sn = JC-8,117Sn =368.5,
J
C-1,119Sn = JC-8,119Sn =385.7 Hz),
[
26]
2
O
3
2
36.75 (flanked by Sn isotope satellites as an incompletely resolved d,
2
O
3
3
2
2
2
J
C-2,117Sn ꢂ JC-7,117Sn ꢂ JC-2,119Sn ꢂ JC-7,119Sn ꢂ9 Hz; C-2, C-7), 147.72 ppm
and 4), we obtained a 93.5:6.5 mixture of 18 (148 mg, 77%, all-E/mono-
Z=95:5) and 2-methyl-6-(tributylstannyl)hepta-1,3,5-triene (5%; isomer-
ic composition unknown) as a colorless oil. H NMR (400.1 MHz, C
6 5 3 c
C D H): d=0.93 (t, J4’,3’ =7.3 Hz, 18H; 6 ꢃ 4’-H ), 1.02 (m , each peak
3
(
flanked by Sn isotope satellites as an incompletely resolved d, JC-3,117Sn
ꢂ
3
3
3
1
J
C-6,117Sn ꢂ JC-3,119Sn ꢂ JC-6,119Sn ꢂ59 Hz; C-3, C-6); IR (film): n˜ =2960, 2925,
6
D
6
/
2
850, 2880, 1605, 1530, 1465, 1415, 1380, 1340, 1295, 1245, 1180, 1155,
ꢀ
1
2
1075, 1045, 1005, 955, 870, 865, 670 cm ; HRMS (Cl, 120 eV): calcd for
flanked by Sn isotope satellites as an incompletely resolved d, J1’-H,117Sn
ꢂ
+
2
C
28
H
53Sn
2
: 629.21912 [M ꢀBu]; found: 629.22022 (+1.7 ppm).
(2E,4E,6E,8E)-2,9-Bis(tributylstannyl)deca-2,4,6,8-tetraene
Following the general procedure, all-E-23 was prepared in THF from bi-
sallylsulfone 22 (250 mg, 0.321 mmol), CBr (123 mL, 270 mg,
(180 mg, 3.20 mmol,
J
1’-H,119Sn ꢂ51 Hz, 6H; 3 ꢃ 1’-H
2 c
), superimposed by 1.02 (m , each peak
2
(all-E-23):
flanked by Sn isotope satellites as an incompletely resolved d, J1’-H,117Sn
ꢂ
2
J
1’-H,119Sn ꢂ50 Hz, 6H; 3 ꢃ 1’-H
2
), 1.38 (qt, J3’,4’ =J3’,2’ =7.3 Hz, 12H; 6 ꢃ
), 1.51–1.72 (m, 12H; 6 ꢃ 2’-H
2
F
2
3
’-H
2
2
), 2.02 (s, flanked by Sn isotope satel-
4
4
1
2 3
.29 mmol, 4.0 equiv), and KOH on Al O
lites as an incompletely resolved d,
CH
Sn isotope satellites as an incompletely resolved d,
J
2-Me,117Sn ꢂ J2-Me,119Sn ꢂ9 Hz, 1H; 2-
4
3
), 2.11 (incompletely resolved q,
J
7,5 =1.4 Hz, each peak flanked by
3
3
J
7-H,117Sn ꢂ J7-H,119Sn
ꢂ47 Hz, 3H; 7-H
3
), 6.17 (s, flanked by Sn isotope satellites as an incom-
2
2
pletely resolved d,
J
1-H,117Sn ꢂ J1-H,119Sn ꢂ66 Hz, 1H; 1-H), 6.51 (d, J3,4
=
1
1
5.3 Hz, 1H; 3-H), 6.58 (d, J5,4 =10.6 Hz, 1H; 5-H), 6.73 ppm (dd, J4.3
=
1
3
5.0, J4,5 =10.6 Hz, 1H; 4-H); C NMR (100.6 MHz, C
6
D
6
/C
6
D
6
): d=9.55
1
(
flanked by Sn isotope satellites as 2 interwoven doublets,
J
C-1’,117Sn
=
[
26]
1
1
0.0 equiv). After flash chromatography
98:2 (v/v), fractions 3 and 4), all-E-23 was ob-
tained as a yellowish oil (157 mg, 69%, all-E/mono-Z=79:21). Following
the general procedure, all-E-23 was also prepared in CH Cl from bisal-
lylsulfone 22 (350 mg, 0.450 mmol), CBr (170 mL, 377 mg, 1.8 mmol,
4.0 equiv), and KOH on Al (252 mg, 4.50 mmol, 10.0 equiv). After
on deactivated Al (5ꢃ2 cm, cyclohexane/
98:2 (v/v), fractions 3 and 4), all-E-23 was obtained as a colorless
2 3
on deactivated Al O (5ꢃ
3
14.6,
lites as 2 interwoven doublets,
C-1’), 13.91 (6 C-4’), 20.21 (3
flanked by Sn isotope satellites as 2 interwoven doublets, JC-3’,117Sn =53.6,
JC-1’,119Sn =329.1 Hz; 3 ꢃ C-1’), 10.61 (flanked by Sn isotope satel-
1
1
J
C-1’,117Sn =325.7,
J
C-1’,119Sn =341.1 Hz; 3 ꢃ
2 cm, cyclohexane/NEt
3
ꢃ
3
ꢃ C-1), 21.01 (3 ꢃ 2-CH ), 27.71
3
(
2
2
3
J
C-3’,119Sn =56.0 Hz; 3 ꢃ C-3’), 27.78 (flanked by Sn isotope satellites as 2
2 2
F
3
3
interwoven doublets,
J
C-3’,117Sn =52.6,
J
C-3’,119Sn =55.0 Hz; 3 ꢃ C-3’), 29.62
2 3
O
2
[26]
(
J
flanked by Sn isotope satellites as an incompletely resolved d, JC-2’,117Sn
ꢂ
flash chromatography
NEt
oil (254 mg, 79%, all-E/mono-Z=83:17). H NMR (400.1 MHz, CDCl
TMS): d=0.89 (t, J4’,3’ =7.3 Hz, 18H; 6 ꢃ 4’-H ), 0.91 (m , 12H; 6 ꢃ 1’-
), 1.31 (qt, J3’,4’ =J3’,2’ =7.3 Hz, 12H; 6 ꢃ 3’-H ), 1.44–1.58 (m, 12H; 6 ꢃ
), 2.02 (d, J1,3 = J10,8 =1.5 Hz, each peak flanked by Sn isotope satel-
2 3
O
2
C-2’,119Sn ꢂ20 Hz; 3 ꢃ C-2’), 29.68 (flanked by Sn isotope satellites as an
3
2
2
1
incompletely resolved d,
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 3
ꢃ
C-2’), 122.38
3
,
3
(
flanked by Sn isotope satellites as an incompletely resolved d,
J
C-4,117Sn
3
c
3
ꢂ63.3, JC-4,119Sn ꢂ67 Hz; C-4), 134.06 (flanked by Sn isotope satellites as 2
H
2
2
1
1
4
4
interwoven doublets,
J
C-1,117Sn =385.6,
J
C-1,119Sn =406.3 Hz; C-1), 138.11
2’-H
lites as an incompletely resolved d,
2
3
3
3
3
(
J
flanked by Sn isotope satellites as 2 interwoven doublets, JC-3,117Sn =69.3,
J
1-H,117Sn ꢂ J10-H,117Sn ꢂ J1-H,119Sn ꢂ
3
3
C-3,119Sn =72.9 Hz; C-3), 140.58 (flanked by Sn isotope satellites as an in-
J
10-H,119Sn ꢂ47 Hz, 6H; 1-H
3 3 c
and 10-H ), 6.26 (m , 2H, 5-H and 6-H), 6.26
(d, J3,4 =J8,7 =12.0 Hz, each peak flanked by Sn isotope satellites as 2 in-
2
2
completely resolved d,
J
C-5,117Sn ꢂ JC-5,119Sn ꢂ31 Hz; C-5), 144.28 (C-6),
6478
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 6469 – 6483

1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
3
3
3
3
terwoven doublets,
2
J
3-H,117Sn = J8-H,117Sn =63.4,
J
3-H,119Sn = J8-H,119Sn =66.7 Hz,
(1E,3E,5E,7E,9E)-1,10-Bis(tributylstannyl)deca-1,3,5,7,9-pentaene (all-E-
29): Following the general procedure, all-E-29 was prepared in THF
1
3
H; 3-H and 8-H), 6.60 ppm (m
100.6 MHz, CDCl , TMS): d=9.32 (flanked by Sn isotope satellites as 2
interwoven doublets,
c
, 2H, 4-H and 7-H); C NMR
(
3
from bisallylsulfone 28 (400 mg, 0.515 mmol), CBr
2 2
F (238 mL, 540 mg,
1
1
J
C-1’,117Sn =316.3,
J
C-1’,119Sn =330.5 Hz;
6
ꢃ
C-1’),
2.58 mmol, 4.0 equiv), and KOH on Al (438 mg, 2.58 mmol,
2 3
O
1
3.80 (6 ꢃ C-4’), 20.16 (C-1, C-10), 27.49 (flanked by Sn isotope satellites
3
3
as 2 interwoven doublets,
JC-3’,117Sn =53.1, JC-3’,119Sn =55.8 Hz; 6 ꢃ C-3’),
2
J
9.26 (flanked by Sn isotope satellites as an incompletely resolved d,
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 6 ꢃ C-2’), 127.39 (C-4, C-7), 132.59 (C-5, C-
2
2
[
26]
6
2
9
), 139.49 (C-3, C-8), 145.43 ppm (C-2, C-9); IR (film): n˜ =3025, 2955,
4.0 equiv). After flash chromatography on deactivated Al
2 3
O (5ꢃ2 cm,
925, 2875, 2850, 1460, 1415, 1375, 1340, 1295, 1180, 1070, 1000, 980, 955,
cyclohexane/NEt 98:2 (v/v), fractions 3–5), all-E-29 was obtained as a
3
ꢀ
1
1
45, 875, 865, 680, 665, 595 cm
;
HRMS (Cl, 120 eV): calcd for
: 714.32085 [M ꢀBu]; found: 714.32120 (+0.5 ppm).
1E,3E,5E,7E)-3-Methyl-1,8-bis(tributylstannyl)nona-1,3,5,7-tetraene (all-
E-26): Following the general procedure, all-E-26 was prepared in THF
from bisallylsulfone 25 (276 mg, 0.354 mmol), CBr (131 mL, 297 mg,
(736 mg, 3.54 mmol,
yellow oil (165.4 mg, 45%, all-E/mono-Z=92:8). H NMR (499.9 MHz,
C D /C D H): d=1.07 (t, J =7.2 Hz, 18H; 6 ꢃ 4’-H ), 1.14 (m , each
+
C
30
H
57Sn
2
6
6
6
5
4’,3’
3
c
peak flanked by Sn isotope satellites as an incompletely resolved d,
(
2
2
J
1’-H,117Sn ꢂ J1’-H,119Sn ꢂ52 Hz, 12H; 6 ꢃ 1’-H
2
), 1.52 (qt, J3’,4’ =J3’,2’ =7.4 Hz,
), 6.28–6.51 (m , 6H, 3-H/
1
2H; 6 ꢃ 3’-H
2
), 1.70–1.82 (m, 12H, 6 ꢃ 2’-H
2
c
2
F
2
8
-H, 4-H/7-H, 5-H/6-H), 6.59 (d, J1,2 =J10,9 =18.6 Hz, each peak flanked
1
.41 mmol, 4.0 equiv), and KOH on Al
2
O
3
2
by Sn isotope satellites as an incompletely resolved d,
J
1-H,117Sn
ꢂ
2
2
2
J
10-H,117Sn ꢂ J1-H,119Sn ꢂ J10-H,119Sn ꢂ70 Hz, 2H; 1-H, 10-H), 6.96 ppm (dd,
J
2,1 =J9,10 =18.6, J2,3 =J9,8 =9.7 Hz, each peak flanked by Sn isotope satel-
3
3
3
lites as
2
interwoven doublets,
J
2-H,117Sn = J9-H,117Sn =57.2,
2-H,119Sn
J =
3
13
J
9-H,119Sn =59.4 Hz, 2H; 2-H, 9-H); C NMR (125.7 MHz, C
6
D
6
/C
6
D
6
): d=
1
[
26]
9.89 (flanked by Sn isotope satellites as 2 interwoven doublets, J
C-1’,117Sn
3
Sn isotope satellites as an incompletely resolved d,
=
1
0.0 equiv). After flash chromatography
on deactivated Al
2
O
3
(5ꢃ
1
27.7, JC-1’,119Sn =343.9 Hz; 6 ꢃ C-1’), 13.92 (6 ꢃ C-4’), 27.70 (flanked by
2
cm, cyclohexane/NEt 98:2 (v/v), fractions 3–5), all-E-26 was obtained
3
3
3
J
C-3’,117Sn ꢂ JC-3’,119Sn
as a yellowish oil (184 mg, 73%, all-E/mono-Z=80:20). Following the
general procedure, all-E-26 was also prepared in CH Cl from bisallylsul-
fone 25 (200 mg, 0.257 mmol), CBr (97.0 mL, 216 mg, 1.03 mmol,
(144 mg, 2.57 mmol, 10.0 equiv). After
on deactivated Al (5ꢃ2 cm, cyclohexane/
ꢂ54 Hz; 6 ꢃ C-3’), 29.57 (flanked by Sn isotope satellites as an incom-
2
2
2
2
pletely resolved d,
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 6 ꢃ C-2’), 132.66 (C-4, C-
2
F
2
7
), 134.15 (C-5, C-6), 135.19 (flanked by Sn isotope satellites as 2 inter-
4
2 3
.0 equiv), and KOH on Al O
1
1
1
1
woven doublets,
J
C-1,117Sn = JC-10,117Sn =368.6,
J
C-1,119Sn = JC-10,119Sn =385.8 Hz;
[
26]
flash chromatography
2 3
O
C-1/C-10), 136.26 (flanked by Sn isotope satellites as an incompletely re-
NEt
3
98:2 (v/v), fractions 3–5), all-E-26 was obtained as a yellowish oil
3
3
3
3
solved
d,
J
C-3,117Sn ꢂ JC-8,117Sn ꢂ JC-3,119Sn ꢂ JC-8,119Sn ꢂ77 Hz;
C-3/C-8),
1
(
159 mg, 76%, all-E/mono-Z=80:20). H NMR (400.6 MHz,
C
6
D
6
/
1
d,
2
1
1
47.77 ppm (flanked by Sn isotope satellites as an incompletely resolved
C
6
D
5
H): d=1.05 (t, J4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H
3
), 1.06 (t, J4’,3’ =7.3 Hz,
2
2
2
2
J
C-2,117Sn ꢂ JC-9,117Sn ꢂ JC-2,119Sn ꢂ JC-9,119Sn ꢂ10 Hz; C-2/C-6); IR (film): n˜ =
9
H; 3 ꢃ 4’-H ), 1.14 (m , each peak flanked by Sn isotope satellites as an
3
c
955, 2925, 2870, 2845, 2360, 2335, 1600, 1555, 1480, 1465, 1420, 1375,
2
2
incompletely resolved d, J1’-H,117Sn ꢂ J1’-H,119Sn ꢂ50 Hz, 6H; 3 ꢃ 1’-H
2
), 1.17
ꢀ1
145, 1095, 1070, 1040, 1005, 875, 860, 760, 690, 670 cm ; HRMS (Cl,
20 eV): calcd for C30
(
m
c
, each peak flanked by Sn isotope satellites as an incompletely re-
+
H
55Sn
2
: 655.23477 [M ꢀBu]; found: 655.23550
2
2
solved d, J1’-H,117Sn ꢂ J1’-H,119Sn ꢂ49 Hz, 6H; 3 ꢃ 1’-H
2
), 1.50 (qt, J3’,4’ =J3’,2’
=
(
+1.1 ppm).
7
.3 Hz, 6H; 3 ꢃ 3’-H
2
), 1.52 (qt, J3’,4’ =J3’,2’ =7.3 Hz, 6H; 3 ꢃ 3’-H
2
), 1.66–
(
1E,3E,5E,7Z,9E)-3,8-Dimethyl-1,10-bis(tributylstannyl)deca-1,3,5,7,9-
1
.84 (m, 12H; 6 ꢃ 2’-H
2
), 1.95 (s, 1H, 3-CH
3
), 2.21 (incompletely re-
pentaene (all-E-32): Following the general procedure, all-E-32 was pre-
4
solved q, J9,7 =1.4 Hz, each peak flanked by Sn isotope satellites as an in-
completely resolved d,
3
3
J
9-H,117Sn ꢂ J9-H,119Sn ꢂ47 Hz, 3H; 9-H
3
), 6.42 (d,
J
4,5 =10.9 Hz, 1H; 4-H), 6.58 (d, J1,2 =19.2 Hz, each peak flanked by Sn
2
2
isotope satellites as 2 interwoven doublets,
J
1-H,117Sn =68.0,
J
1-H,119Sn
4
=
=
=
7
1
1
0.5 Hz, 1H; 1-H), 6.76 (incompletely resolved qd, J7,6 =10.7, J
7,9
.6 Hz, 1H; 7-H), 6.79 (dd, J5,6, J5,4 =11.1 Hz, 1H; 5-H), 6.90 (dd, J6,5
2 2
pared in THF from bisallylsulfone 31 (90.0 mg, 0.112 mmol), CBr F
(
0.12 mL, 90 mg, 0.4 mmol, 3.9 equiv), and KOH on Al
2
O
3
(381 mg,
4.1, J6,7 =11.1 Hz, 1H; 5-H), 7.05 ppm (d, J2,1 =19.2 Hz, 1H; 2-H);
[
26]
1
3
2.21 mmol, 19.7 equiv). After flash chromatography
on deactivated
C NMR (100.6 MHz, C
6
D
6
/C
6
D
6
1
): d=9.60 (flanked by Sn isotope satel-
1
2 3 3
Al O (5ꢃ2.5 cm, cyclohexane/NEt 100:1 (v/v), fractions 2 and 3), all-E-
lites as 2 interwoven doublets,
J
C-1’,117Sn =314.8,
J
C-1’,119Sn =329.3 Hz; 3 ꢃ
3
2 was obtained as a yellow oil (59.2 mg, 71%, all-E/mono-Z=84:16).
C-1’), 9.96 (flanked by Sn isotope satellites as 2 interwoven doublets,
1
1
1
H NMR (499.9 MHz, C
.10 (m, 12H; 6 ꢃ 1’-H ), superimposes 0.92 (t, Jvic =7.3 Hz, 18H; 6 ꢃ 4’-
), 1.33–1.44 (m, approximately interpretable as 1.40, tq, both Jvic
6
D
6
/C
6
HD
5
; sample not entirely pure): d=ꢂ0.90–
J
C-1’,117Sn =326.4, JC-1’,119Sn =342.1 Hz; 3 ꢃ C-1’), 12.26 (3-CH
3
), 13.95 (3 ꢃ
1
H
2
C-4’), 13.96 (3 ꢃ C-4’), 20.35 (flanked by Sn isotope satellites as an in-
2
2
3
=
completely resolved d, JC-9,117Sn ꢂ JC-9,119Sn ꢂ39 Hz; C-9), 27.77 (flanked by
3
3
7.3 Hz, 12H; 6 ꢃ 3’-H
CH and 8-CH ), 6.26 (brm
isotope satellites not unambiguously identified because of impurity, 2H;
-H and 10-H), 6.62 (m , 2H; 5-H and 6-H), 6.93 ppm (d, J2,1 =19.1 Hz,
each peak flanked by Sn isotope satellites as an incompletely resolved d,
2
), 1.52–1.70 (m, 12H; 6 ꢃ 2’-H
2
), 1.87 (s, 2H; 3-
Sn isotope satellites as 2 interwoven doublets, C-3’,117Sn =52.9, J =
J
C-3’,119Sn
3
3
c
, 2H; 4-H and 7-H), 6.50 (d, J1,2 =19.2 Hz, Sn
5
5.0 Hz; 3 ꢃ C-3’), 27.83 (flanked by Sn isotope satellites as 2 interwoven
3
3
doublets,
J
C-3’,117Sn =52.9,
J
C-3’,119Sn =55.3 Hz; 3 ꢃ C-3’), 29.64 (flanked by
1
c
2
2
Sn isotope satellites as an incompletely resolved d,
J
C-2’,117Sn ꢂ JC-2’,119Sn
ꢂ20.0 Hz; 3 ꢃ C-2’), 29.66 (flanked by Sn isotope satellites as an incom-
3
3
13
J
117Sn,H ꢂ J119Sn,H ꢂ65 Hz, 2H; 2-H and 9-H); C NMR (125.7 MHz, C
6 6
D /
2
2
pletely resolved d,
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 3 ꢃ C-2’), 128.12 (C-1),
C
6
D
6
): d=9.95 (flanked by Sn isotope satellites as 2 interwoven doublets,
117Sn, C-1’ = J117Sn, C-1’’ =326.7,
1
28.76 (C-6), 129.31 (flanked by Sn isotope satellites as an incompletely
1
1
1
1
J
J
119Sn, C-1’ = J119Sn, C-1’’ =342.1 Hz, 6
ꢃ
C-1’),
4
4
resolved d, JC-5,117Sn ꢂ JC-5,119Sn ꢂ7 Hz; C-5), 132.57 (flanked by Sn isotope
1
2.26 (3-CH
3 3
, 8-CH ), 13.92 (6 ꢃ C-4’), 27.73 (flanked by Sn isotope sat-
4
4
satellites as 2 interwoven doublets, C-4,119Sn =8.0 Hz; C-4),
J
C-4,117Sn =6.0,
J
3
3
3
ellites as an incompletely resolved d,
J
117Sn, C-3’ ꢂ J117Sn, C-3’’ ꢂ J119Sn, C-3’ ꢂ
1
J
37.20 (flanked by Sn isotope satellites as
C-3,117Sn =65.9, JC-3,119Sn =68.6 Hz; C-3), 140.67 (flanked by Sn isotope sat-
2
interwoven doublets,
3
J
119Sn, C-3’’ ꢂ54 Hz, 6 ꢃ C-3’), 29.61 (flanked by Sn isotope satellites as an
3
3
2 2 2 2
incompletely resolved d,
J
117Sn, C-2’ ꢂ J117Sn, C-2’’ ꢂ J119Sn, C-2’ ꢂ J119Sn,C-2’’
’
2
2
ellites as an incompletely resolved d,
1
pletely resolved d,
2
8
6
J
C-7,117Sn ꢂ JC-7,119Sn ꢂ30 Hz; C-7),
ꢂ21 Hz, 6 ꢃ C-2’), 128.26 (seemingly flanked by Sn isotope satellites as
1
1
1
1
45.08 (C-8), 151.67 ppm (flanked by Sn isotope satellites as an incom-
an incompletely resolved d,
J
117
ꢂ J117
ꢂ J119
ꢂ J119
Sn,C-1
Sn,C-10
Sn,C-1
Sn,C-10
2
2
J
C-2,117Sn ꢂ JC-2,119Sn ꢂ11 Hz; C-2); IR (film): n˜ =2960,
ꢂ324 Hz; C-1, C-10), 130.94 (C-5, C-6), 132.62 (C-4, C-7), 137.06 (C-3,
925, 2885, 2850, 1460, 1415, 1380, 1075, 1045, 1020, 1005, 980, 965, 945,
C-8), 151.58 ppm (flanked by Sn isotope satellites as an incompletely re-
ꢀ1
2
2
2
2
75, 860, 765, 680, 66, 590 cm ; HRMS (Cl, 120 eV): calcd for C30
57.25042 [M ꢀBu]; found: 657.25000 (ꢀ0.6 ppm).
H
57Sn
2
:
solved d, J
(EI, 70 eV): calcd for C32
117Sn,C-2
ꢂ J
117Sn,C-9
ꢂ J
119Sn,C-2
ꢂ J
119Sn,C-9
ꢂ11 Hz; C-2, C-9); HRMS
+
+
H
59Sn
2
: 683.26607
A[ M ꢀBu]; found: 683.26266
H
U
G
R
N
N
Chem. Eur. J. 2011, 17, 6469 – 6483
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6479

R. Brꢁckner et al.
2 3 3
on deactivated Al O (5ꢃ2 cm, cyclohexane/NEt 98:2 (v/v), fractions 2
5
6
(
ꢀ5.0 ppm). The E configuration of the C =C double bond was shown
) in which the
by an edited HSQC spectrum (499.9/125.7 MHz, CDCl
C NMR resonance at d=130.84 ppm (C-5, C-6) was split by
C-6,6-H =152.4 Hz, such that both the low- and the highfield branch re-
vealed splittings due to J4,3 =J5,6 =11.9 and J4,5 =14.4 Hz.
3
and 3) provided mono-Z-12 as a colorless oil (126 mg, 53%, mono-Z/all-
1
3
1
1
J
C-5,5-H
=
E=82:18). H NMR (400.1 MHz, CDCl
9H; 3 ꢃ 4’-H ), 0.94 (t, J4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H
1’-H ), 1.02 (m , 6H; 3 ꢃ 1’-H ), 1.31–1.44 (m, 12H; 6 ꢃ 3’-H
m, 12H; 6 ꢃ 2’-H ), 2.03 (s, flanked by Sn isotope satellites as an incom-
3
, TMS): d=0.93 (t, J4’,3’ =7.3 Hz,
), 0.99 (m , 6H; 3 ꢃ
), 1.50–1.68
1
J
3
3
c
2
c
2
2
(
2
4
Synthesis of mono-Z-polyene distannanes:
4
pletely resolved d, J2-Me,117Sn ꢂ J2-Me,119Sn ꢂ10 Hz, 1H; 2-CH
3
), 5.98 (d, J3,4 =
General procedure for (Sylvestre–)Julia polyene synthesis: KHMDS
1.0m, 1.2 equiv) in THF was added dropwise to a solution of the alde-
1
1.6 Hz, 1H; 3-H), 6.10 (dd, J4,3 =J4,5 =11.0 Hz, 1H; 4-H), 6.20 (s, flanked
(
2
2
by Sn isotope satellites as an incompletely resolved d,
J
1-H,117Sn ꢂ J1-H,119Sn
hyde (~0.1m) and benzothiazolylsulfone (1.28 equiv) in THF at ꢀ788C.
ꢂ71 Hz, 1H; 1-H), 6.45 (d, J6,5 =18.6 Hz, each peak flanked by Sn iso-
After the reaction mixture was alowed to warm to room temperature
2
2
tope satellites as an incompletely resolved d,
J
6-H,117Sn ꢂ J6-H,119Sn ꢂ74 Hz,
overnight, tBuOMe and H
ed and the aqueous phase extracted with tBuOMe (2ꢃ). The combined
etheral phases were dried over Na SO , the solvent was removed under
reduced pressure, and the residue purified by chromatography on neutral
alumina (deactivated by 3% H O).
(1E,3Z,5E)-1,6-Bis(tributylstannyl)hepta-1,3,5-triene (mono-Z-9): Fol-
2
O were added. The organic phase was separat-
1
H; 6-H), 7.43 ppm (dd, J5,6 =18.8, J5,4 =10.5 Hz, each peak flanked by
Sn isotope satellites as an incompletely resolved d,
3
3
J
5-H,117Sn ꢂ J5-H,119Sn
2
4
13
ꢂ60 Hz, 1H; 5-H); C NMR (100.6 MHz, CDCl
3 3
/CDCl ): d=9.88
1
(
3
C-1’,117Sn
flanked by Sn isotope satellites as 2 interwoven doublets, J =
2
1
27.7, JC-1’,119Sn =342.6 Hz; 3 ꢃ C-1’), 10.50 (flanked by Sn isotope satel-
lites as 2 interwoven doublets,
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
1
1
JC-1’,117Sn =324.7, JC-1’,119Sn =339.7 Hz; 3 ꢃ
lowing the general procedure, mono-
Z-9 was prepared from aldehyde 4
C-1’), 13.91 (6 ꢃ C-4’), 27.23 (2-Me), 27.70 (flanked by Sn isotope satel-
3
3
lites as 2 interwoven doublets,
JC-3’,117Sn =52.2, JC-3’,119Sn =54.6 Hz; 3 ꢃ C-
(
69.1 mg, 0.200 mmol), benzothiazolyl-
sulfone 10 (128.6 mg, 0.237 mmol,
.18 equiv), and KHDMS (1.00 equiv).
Flash chromatography on deactivated Al (5ꢃ2.5 cm, cyclohexane/
NEt 50:1 (v/v), fractions 3 and 4), provided mono-Z-9 as a yellow oil
74.9 mg, 56%, mono-Z/all-E=95:5). H NMR (499.9 MHz, CDCl
TMS): d=0.85–0.95 (m, 12H, 6 ꢃ 1’-H ), superimposes 0.89 and 0.90 (2ꢃ
t, Jvic =7.3 Hz, 18H; 6 ꢃ 4’-H ), 1.316 and 1.325 (2ꢃm , approximately in-
terpretable as 2ꢃtq, each time both Jvic =7.3 Hz, 12H; 6 ꢃ 3’-H ), 1.44–
), 2.02 (d, J7,5 =1.9 Hz, each peak flanked by Sn
isotope satellites as an incompletely resolved d,
H; 7-H ), 5.95 (ddd, J3,4 =J3,2 =10.8, J3,1 or J3,5 =0.5 Hz, 1H; 3-H), 6.27
, J4,3 =J4,5 =11.2 Hz, 1H; 4-H), 6.33 (d, J1,2 =18,6 Hz, each peak
flanked by Sn isotope satellites as an incompletely resolved d,
c
, tentatively interpretable as dqd,
5,4 =11.3, J5,7 =1.7, J5,3 =1.1 Hz, each peak flanked by Sn isotope satel-
3
J
’), 27.74 (flanked by Sn isotope satellites as 2 interwoven doublets,
C-3’,117Sn =54.3, JC-3’,119Sn =57.0 Hz; 3 ꢃ C-3’), 29.59 (3 ꢃ C-2’,), 29.69 (3 ꢃ
3
3
1
C-2’), 131.74 (flanked by Sn isotope satellites as 2 interwoven doublets,
[
26]
3
3
2
O
3
J
C-4,117Sn =74.1, JC-4,119Sn =77.0 Hz; C-4), 132.81 (flanked by Sn isotope sat-
1
1
3
ellites as 2 interwoven doublets, J
C-1,117Sn
=375.7, J
C-1,119Sn
=393.5 Hz; C-1),
1
(
3
,
133.94 (flanked by Sn isotope satellites as
2
interwoven doublets,
3
3
2
JC-3,117Sn =62.8, J
C-3,119Sn
=65.4 Hz; C-3), 135.61 (flanked by Sn isotope sat-
1
1
3
c
ellites as 2 interwoven doublets, J
C-6,117Sn
=372.3, J
C-6,119Sn
=389.7 Hz; C-6),
2
144.52 (flanked by Sn isotope satellites as an incompletely resolved d,
4
2
2
1
.57 (m, 12H; 6 ꢃ 2’-H
2
JC-5,117Sn ꢂ J
C-5,119Sn
ꢂ12 Hz; C-5), 151.23 ppm (flanked by Sn isotope satel-
3
3
2
2
J
117Sn,H ꢂ J119Sn,H ꢂ47 Hz,
lites as an incompletely resolved d,
HRMS spectrum was obtained because the compound did not stand up
to the ionization conditions.
J
117 ꢂ J 119 ꢂ7 Hz; C-2); no
C-2, Sn
C-2, Sn
3
4
4
1
(
ddm
c
2
J
117Sn,H
ꢂ
AHCTUNGTRENNUNG
2
J
119Sn,H ꢂ72 Hz, 1H; 1-H), 6.75 (dm
4
4
J
1
6
(107.0 mg, 0.297 mmol, 1.08 equiv), benzothiazolylsulfone 10
3
3
lites as an incompletely resolved d,
7
J
117Sn,H ꢂ J119Sn,H ꢂ67 Hz, 1H; 5-H),
(
(
148.8 mg, 0.274 mmol), and KHMDS
1.02 equiv). Flash chromatography
4
.08 ppm (ddd, J2,1 =18.5, J2,3 =10.7,
J
2,4 =1.0 Hz, each peak flanked by
[26]
3
3
Sn isotope satellites as 2 interwoven doublets,
9.8 Hz, 1H; 2-H); C NMR (125.7 MHz, CDCl
flanked by Sn isotope satellites as 2 interwoven doublets,
15.8, JC-1’’,119Sn =330.1 Hz, 3 ꢃ C-1’’)*, 9.57 (flanked by Sn isotope satel-
J
117Sn,H =57.5,
119Sn,H
J =
on deactivated Al
clohexane/NEt 100:2 (v/v), fractions
–6) provided mono-Z-15 as a yellow
oil (111.9 mg, 64%, mono-Z/all-E=
5:5). H NMR (499.9 MHz, CDCl
, TMS): d= ꢂ0.86–0.98 (m, 12H; 6 ꢃ
’-H ), superimposes 0.89 (t, Jvic =7.3 Hz, 18H; 6 ꢃ 4’-H ), 1.32 (tq, both
), 1.43–1.58 (m, 12H; 6 ꢃ 2’-H ), 2.03 (d,
2 3
O (5ꢃ2.5 cm, cy-
1
3
5
(
3
3 3
/CDCl ): d=9.25
3
1
C-1’’,117Sn
J =
4
1
1
1
lites as 2 interwoven doublets,
J
C-1’,117Sn =329.1,
J
C-1’,119Sn =344.5 Hz, 3 ꢃ
1
9
1
3
C-1’)*, 13.71 (3 ꢃ C-4’ + 3 ꢃC-4’’), 19.68 (C-7), 27.29 (flanked by Sn iso-
tope satellites as an incompletely resolved d,
ꢃ C-3’’)*, 27.41 (flanked by Sn isotope satellites as an incompletely re-
2
3
3
3
J
C-3’’,117Sn ꢂ JC-3’’,119Sn ꢂ55 Hz,
J
vic =7.3 Hz, 12H; 6 ꢃ 3’-H
2
2
3
4
4
J
1,3 = J8,6 =1.7 Hz, each peak flanked by Sn isotope satellites as an in-
3
3
solved d, JC-3’,117Sn ꢂ JC-3’,119Sn ꢂ58 Hz, 3 ꢃ C-3’)*, 29.12 (flanked by Sn iso-
3
3
completely resolved d,
m , 2H, 4-H and 5-H), 6.76 ppm (m , each peak flanked by Sn isotope
c c
satellites as an incompletely resolved d, J117Sn,H ꢂ J119Sn,H ꢂ67 Hz, 2H; 3-H
and 6-H); C NMR (125.7 MHz, CDCl /CDCl ): d=9.26 (flanked by Sn
isotope satellites as 2 interwoven doublets,
330.3 Hz; 6 ꢃ C-1’), 13.70 (6 ꢃ C-4’), 19.69 (C-1, C-8), 27.40 (flanked by
J
117Sn,H ꢂ J119Sn,H ꢂ45.1 Hz, 6H; 1-H
3 3
, 8-H ), 6.32
2
2
tope satellites as an incompletely resolved d,
J
C-2’’,117Sn ꢂ JC-2’’,119Sn ꢂ21 Hz,
(
3
ꢃ C-2’’)**, 29.17 (flanked by Sn isotope satellites as an incompletely
3
3
2
2
1
3
resolved d, JC-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz, 3 ꢃ C-2’)**, 122.16 (flanked by Sn
3
3
3
3
1
1
isotope satellites as an incompletely resolved d,
J
C-4,117Sn ꢂ JC-4,119Sn
J
C-1’,117Sn =315.5,
C-1’,119Sn
J =
ꢂ63 Hz; C-4), 130.76 (flanked by Sn isotope satellites as an incompletely
3
3
3
3
resolved d, JC-3,117Sn ꢂ JC-3,119Sn ꢂ74 Hz; C-3), 134.04 (flanked by Sn isotope
Sn isotope satellites as an incompletely resolved d, JC-3’,117Sn ꢂ J
C-3’,119Sn
2
2
satellites as an incompletely resolved d,
J
C-5,117Sn ꢂ JC-5,119Sn ꢂ31 Hz; C-5),
ꢂ55 Hz; 6 ꢃ C-3’), 29.17 (flanked by Sn isotope satellites as an incom-
2
2
1
36.15 (flanked by Sn isotope satellites as
2
interwoven doublets,
pletely resolved d,
J
117 ꢂ J
119 ꢂ20 Hz; 6 ꢃ C-2’), 121.89 (flanked
3 3
117
C-2’, Sn
C-2’, Sn
1
1
J
C-1,117Sn =363.0,
J
C-1,119Sn =380.0 Hz; C-1), 141.87 (flanked by Sn isotope
by Sn isotope satellites as an incompletely resolved d, J 117 ꢂ J
ꢂ
C-4, Sn
C-5, Sn
2
2
3
3
satellites as an incompletely resolved d,
46.56 ppm (C-6); *SnCH CH CH CH
J
C-2,117Sn ꢂ JC-2,119Sn ꢂ10 Hz; C-2),
JC-4,119Sn ꢂ J
C-5,119Sn
ꢂ64 Hz; C-4, C-5), 134.05 (flanked by Sn isotope satel-
2
2
2
2
1
2
2
2
3
resonances were distinguished
lites as an incompletely resolved d,
J
117 ꢂ J
117 ꢂ J
119 ꢂ J
C-6, Sn
119
C-3, Sn
C-6, Sn
C-3, Sn
based on the observation that this nucleus is shifted towards higher field
in the a-CH group rather than a-H-substituted alkenylstannanes and
that the corresponding
changeable; IR (film): n˜ =2955, 2925, 2870, 2855, 1465, 1375, 1070, 990,
ꢂ20 Hz; C-3, C-6), 146.33 ppm (C-2, C-7). The Z configuration of the
4 5
3
C =C double bond was shown by an edited HSQC spectrum (499.9/
1
13
J
C,118Sn value is smaller; **assignments are inter-
125.7 MHz, CDCl ) in which the C NMR resonance d=121.89 (C-4, C-
3
1
1
5) was split by JC-4,4-H = J
C-5,5-H
=154.3 Hz, such that both the low- and
ꢀ1
8
C
75, 865, 820, 690, 665, 595, 535 cm ; HRMS (EI, 70 eV): calcd for
: 617.21912 [M ꢀBu]; found: 617.22040 (+2.1 ppm).
ACHTUNGTRENNUNG( 1E,3Z,5E)-2-Methyl-1,6-bis(tributylstannyl)hexa-1,3,5-triene (mono-Z-
2): Following the general procedure, mono-Z-12 was prepared from al-
dehyde 13 (126 mg, 0.351 mmol), ben-
highfield branch revealed splittings due to J4,5 ꢂJ ꢂJ ꢂJ ꢂ11.5 Hz;
4,3
5,4
5,6
+
27
H
53Sn
2
IR (film): n˜ =2955, 2925, 2870, 2855, 1465, 1375, 1070, 960, 875, 770, 690,
ꢀ
1
6
65 cm ; HRMS (EI, 70 eV): calcd for C28
H
55Sn
2
, 67% intensity rather
+
than 100% intensity isotopomer): 631.23478 [M ꢀBu]; found: 631.23649
1
(
+2.7 ppm).
zothiazolylsulfone
3
(222 mg,
(1E,3Z,5E,7E)-1,8-Bis(tributylstannyl)octa-1,3,5,7-tetraene (mono-Z-20):
Following the general procedure, mono-Z-20 was prepared from alde-
0.421 mmol, 1.2 equiv), and KHMDS
[
26]
(1.2 equiv). Flash chromatography
hyde
4
(100 mg, 0.265 mmol), benzothiazolylsulfone 21 (168 mg,
6480
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 6469 – 6483

1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
3
J
3-H,119Sn =66.4 Hz, 1H; 3-H), 6.37 (dd, J7,8 =J7,6 =11.2 Hz, 1H; 7-H), 6.66
(
dd, J4,5 =14.8, J4,3 =10.5 Hz, 1H; 4-H), 6.72 (dd, J5,4 =14.7, J5,6 =10.6 Hz,
1
H; 5-H), 6.72 (dd, J5,4 =14.7, J5,6 =10.6 Hz, 1H; 5-H), 6.79 ppm (d, J8,7
=
1
1.4 Hz, each peak flanked by Sn isotope satellites as an incompletely re-
3
3
13
solved d,
J
8-H,117Sn ꢂ J8-H,119Sn ꢂ66 Hz, 1H; 8-H); C NMR (100.6 MHz,
3
CDCl , TMS): d=9.31 (flanked by Sn isotope satellites as 2 interwoven
doublets, JC-1’,117Sn =316.0, JC-1’,119Sn =331.0 Hz; 3 ꢃ C-1’), 9.41 (flanked by
Sn isotope satellites as 2 interwoven doublets, JC-1’,117Sn =315.3, JC-1’,119Sn =
1
1
0
.318 mmol, 1.2 equiv), and KHMDS (1.0 equiv). Flash chromatogra-
[
26]
1
1
phy on deactivated Al
2
O
3
(5ꢃ2 cm, cyclohexane/NEt
3
98:2 (v/v), frac-
tions 2 and 3) provided mono-Z-20 as a colorless oil (132 mg, 73%,
329.8 Hz; 3 ꢃ C-1’), 13.78 (3 ꢃ C-4’), 13.80 (3 ꢃ C-4’), 19.82 (flanked by
1
2
2
mono-Z/all-Eꢃ96:4). H NMR (400.1 MHz, C
.3 Hz, 9H; 3 ꢃ 4’-H ), 0.92 (t, J4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H
each peak flanked by Sn isotope satellites as 2 interwoven doublets,
6
D
6
/C
6
D
5
H): 0.92 (t, J4’,3’
=
Sn isotope satellites as an incompletely resolved d,
J
C-1,117Sn ꢂ JC-1,119Sn
7
3
3
), 0.97 (m
c
,
ꢂ38 Hz; C-10), 20.19 (flanked by Sn isotope satellites as an incompletely
2
2
resolved d, JC-1,117Sn ꢂ JC-1,119Sn ꢂ36 Hz; C-1), 27.48 (flanked by Sn isotope
2
2
3
3
J
1’-H,117Sn =50.0,
J
1’-H,119Sn =52.5 Hz, 6H; 3 ꢃ 1’-H
2
), 0.97 (m
c
, each peak
satellites as 2 interwoven doublets, JC-3’,117Sn =52.9, JC-3’,119Sn =55.3 Hz; 3 ꢃ
C-3’), 27.51 (flanked by Sn isotope satellites as 2 interwoven doublets,
2
flanked by Sn isotope satellites as 2 interwoven doublets, J1’-H,117Sn =49.0,
2
3
3
J
’-H
1’-H,119Sn =51.8 Hz, 6H; 3 ꢃ 1’-H
2
), 1.35 (qt, J3’,4’ =J3’,2’ =7.3 Hz, 6H; 3 ꢃ
), 1.36 (qt, J3’,4’ =J3’,2’ =7.3 Hz, 6H; 3 ꢃ 3’-H ), 1.47–1.68 (m, 12H; 6
), 6.00 (dd, J5,6 =J5,4 =11.4 Hz, 1H; 5-H), 6.12 (dd, J6,7 =J6,5
J
C-3’,117Sn =53.1, JC-3’,119Sn =55.3 Hz; 3 ꢃ C-3’), 29.26 (flanked by Sn isotope
2
2
3
ꢃ
2
2
satellites as an incompletely resolved d,
C-2’), 29.31 (flanked by Sn isotope satellites as an incompletely resolved
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 3 ꢃ
2’-H
2
=
2
2
1
J
0.7 Hz, 1H; 6-H), 6.29 (dd, J3,4 =14.6, J3,2 =10.3 Hz,1H; 3-H), 6.44 (d,
1,2 =18.7 Hz, each peak flanked by Sn isotope satellites as 2 interwoven
d, JC-2’,117Sn ꢂ J
C-2’,119Sn
ꢂ20 Hz; 3 ꢃ C-2’), 123.62 (flanked by Sn isotope
3
3
satellites as an incompletely resolved d,
J
C-7, Sn
117 ꢂ J 119 ꢂ65 Hz; C-7),
C-7, Sn
2
2
doublets,
J
1-H,117Sn =69.2,
J
1-H,119Sn =72.5 Hz, 1H; 1-H), 6.47 (d,
J
8,7
=
127.21 (C-5), 128.10 (flanked by Sn isotope satellites as 2 interwoven
doublets, JC-4,117Sn =62.8, JC-4,119Sn =66.2 Hz; C-4), 128.59 (C-6), 134.41
3
3
1
8.6 Hz, 1H, 8-H), 6.82 (dd, J2,1 =18.6, J2,3 =10.2 Hz, each peak flanked
3
3
2
by Sn isotope satellites as an incompletely resolved d,
J
2-H,117Sn ꢂ J2-H,119Sn
(flanked by Sn isotope satellites as an incompletely resolved d, J
C-8,117Sn
ꢂ
2
ꢂ59 Hz, 1H; 2-H), 6.95 (dd, J4,3 =14.7, J4,5 =11.7 Hz, 1H; 4-H), 7.34 ppm
JC-8,119Sn ꢂ31 Hz; C-8), 139.53 (flanked by Sn isotope satellites as an in-
2
2
(
dd, J7,8 =18.5, J7,6 =10.7 Hz, each peak flanked by Sn isotope satellites as
completely resolved d,
(flanked by Sn isotope satellites as 4 interwoven doublets, JC-2,117Sn =
385.8*, JC-9,117Sn =387.7**, JC-2,119Sn =403.7*, JC-9,119Sn =405.1 Hz**; C-2, C-
9); *,**assignments interchangeable; IR (film): n˜ =3025, 2960, 2925,
2870, 2855, 1685, 1455, 1415, 1375, 1360, 1340, 1295, 1245, 1185, 1150,
J
117 ꢂ J 119 ꢂ30 Hz; C-3), 146.25 ppm
C-3, Sn
C-3, Sn
3
3
1
an incompletely resolved d,
J
7-H,117Sn ꢂ J7-H,119Sn ꢂ59 Hz, 1H; 7-H);
1
3
1
1
1
C NMR (100.6 MHz, C
6
D
6
/C
6
D
6
): d=9.85 (flanked by Sn isotope satel-
1
1
lites as 2 interwoven doublets,
J
C-1’,117Sn =332.9, JC-1’,119Sn =339.2 Hz; 3 ꢃ
C-1’), 9.88 (flanked by Sn isotope satellites as 2 interwoven doublets,
1
1
ꢀ1
J
C-1’,117Sn =332.7,
J
C-1’,119Sn =339.2 Hz; 3 ꢃ C-1’), 13.89 (6 ꢃ C-4’), 27.65
1075, 1045, 1015, 1005, 955, 940, 875, 840, 770, 690, 665, 595 cm ; HRMS
3
+
(
flanked by Sn isotope satellites as 2 interwoven doublets, JC-3’,117Sn =52.9,
C-3’,119Sn =54.8 Hz; 6 ꢃ C-3’), 27.66 (flanked by Sn isotope satellites as 2
(Cl, 120 eV): calcd for C H Sn : 712.32026 [M ]; found: 712.31970
3
4
66
2
3
J
(ꢀ0.8 ppm).
3
3
interwoven doublets,
(
J
C-3’,117Sn =52.6,
J
C-3’,119Sn =55.0 Hz; 6 ꢃ C-3’), 29.53
(
(
1E,3E,5Z,7E)-3-Methyl-1,8-bis(tributylstannyl)nona-1,3,5,7-tetraene
mono-Z-26): Following the general procedure, mono-Z-26 was prepared
2
flanked by Sn isotope satellites as an incompletely resolved d, JC-2’,117Sn
ꢂ
2
J
C-2’,119Sn ꢂ21 Hz; 3 ꢃ C-2’), 29.54 (flanked by Sn isotope satellites as an
incompletely resolved d, JC-2’,117Sn ꢂ JC-2’,119Sn ꢂ21 Hz; 3 ꢃ C-2’), 127.54 (C-
), 128.83 (C-5), 133.41 (flanked by Sn isotope satellites as 2 interwoven
from aldehyde 27 (219 mg, 0.567 mmol), benzothiazolylsulfone 10
400 mg, 0.737 mmol, 1.3 equiv), and KHMDS (1.28 equiv). Flash chro-
2
2
(
4
[26]
2 3 3
matography on deactivated Al O (5ꢃ2 cm, cyclohexane/NEt 98:2 (v/
4
4
doublets, JC-6,117Sn =72.4, JC-6,119Sn =75.3 Hz; C-6), 135.96 (C-1), 136.50 (C-
8
), 137.23 (C-3), 142.61 (flanked by Sn isotope satellites as an incom-
2
2
pletely resolved d,
by Sn isotope satellites as an incompletely resolved d,
J
C-7,117Sn ꢂ JC-7,119Sn ꢂ10 Hz; C-7), 147.63 ppm (flanked
2
2
J
C-2,117Sn ꢂ JC-2,119Sn
ꢂ9 Hz; C-2); IR (film): n˜ =3020, 2960, 2925, 2875, 2850, 1600, 1525,
1
8
465, 1455, 1420, 1380, 1360, 1340, 1295, 1250, 1075, 1005, 990, 960, 875,
ꢀ
1
65, 820, 690, 665, 595, 570 cm
;
HRMS (Cl, 120 eV): calcd for
: 627.21853 [M ꢀBu]; found: 627.21960 (+1.7 ppm).
2E,4Z,6E,8E)-2,9-Bis(tributylstannyl)deca-2,4,6,8-tetraene (mono-Z-23):
v), fractions 2–4) povided mono-Z-26 as a colorless oil (294 mg, 73%,
+
1
28 2
C H53Sn
mono-Z/all-Eꢃ96:4). H NMR (400.1 MHz, CDCl
4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H ), 0.84 (t, J4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H
imposes 0.85 (m , each peak flanked by Sn isotope satellites as 2 interwo-
, TMS): d=0.83 (t,
3
(
J
3
3
), super-
Following the general procedure, mono-Z-23 was prepared from alde-
hyde 24 (234 mg, 0.608 mmol), benzothiazolylsulfone 10 (421 mg,
c
2
2
ven doublets, J1’-H,117Sn =50.4, J1’-H,119Sn =52.0 Hz, 6H; 3 ꢃ 1’-H
2
), 0.87 (m
c
,
0
.776 mmol, 1.28 equiv), and KHMDS (1.28 equiv). Flash chromatogra-
each peak flanked by Sn isotope satellites as 2 interwoven doublets,
[
26]
2
2
phy on deactivated Al
2
O
3
(5ꢃ2 cm, cyclohexane/NEt
3
98:2 (v/v), frac-
J
1’-H,117Sn =49.0,
J
1’-H,119Sn =50.8 Hz, 6H; 3 ꢃ 1’-H
2
), 1.25 (qt, J3’,4’ =J3’,2’ =
7
1
.0 Hz, 6H; 3 ꢃ 3’-H
.52 (m, 12H; 6 ꢃ 2’-H
2
), 1.27 (qt, J3’,4’ =J3’,2’ =7.0 Hz, 6H; 3 ꢃ 3’-H
2
), 1.40–
3
), 1.82 (s, 1H; 3-CH ), 1.96 (d, J9,7 =1.4 Hz, each
4
2
peak flanked by Sn isotope satellites as an incompletely resolved d,
3
3
J
9-H,117Sn ꢂ J9-H,119Sn ꢂ47 Hz, 3H; 9-H
3
), 6.24 (dd, J5,4 =J5,6 =11.3 Hz, 1H; 5-
H), superimposes 6.24 (d, J1,2 =18.9 Hz, each peak flanked by Sn isotope
satellites as 2 interwoven doublets, J1-H,117Sn =65.7, J1-H,119Sn =67.7 Hz, 1H;
2
2
tions 2–4) provided mono-Z-23 as a colorless oil (276 mg, 64%, mono-Z/
1
4
-H), 6.32 (dd, J6,7 =J6,5 =11.2 Hz, 1H; 6-H), 6.48 (d, J4,5 =11.7 Hz, 1H;
-H), 6.58 (d, J2,1 =19.2 Hz, each peak flanked by Sn isotope satellites as
1
all-Eꢃ96:4). H NMR (400.1 MHz, CDCl
3
, TMS): d=0.95 (t, J4’,3’
=
7
.3 Hz, 9H; 3 ꢃ 4’-H
3
), 0.96 (t, J4’,3’ =7.3 Hz, 9H; 3 ꢃ 4’-H ), 0.97 (m
3
c
,
3
3
an incompletely resolved d,
J
2-H,117Sn ꢂ J2-H,119Sn ꢂ63 Hz, 1H; 2-H),
each peak flanked by Sn isotope satellites as an incompletely resolved d,
4
6
.71 ppm (dd, J7,6 =11.1,
J
7,9 =1.6 Hz, each peak flanked by Sn isotope
2
2
J
1’-H,117Sn ꢂ J1’-H,119Sn ꢂ51 Hz, 6H; 3 ꢃ 1’-H
2
), 0.99 (m
c
, each peak flanked
3
3
satellites as an incompletely resolved d, J7-H,117Sn ꢂ J7-H,119Sn ꢂ64.4 Hz, 1H;
-H); C NMR (100.6 MHz, CDCl , TMS): d=8.31 (flanked by Sn iso-
tope satellites as interwoven doublets, JC-1’,117Sn =315.6, JC-1’,119Sn
330.4 Hz; 3 ꢃ C-1’), 8.55 (flanked by Sn isotope satellites as 2 interwoven
2
2
1
3
by Sn isotope satellites as an incompletely resolved d, J1’-H,117Sn ꢂ J1’-H,119Sn
7
3
1
1
ꢂ51 Hz, 6H; 3 ꢃ 1’-H
2
), 1.37 (qt, J3’,4’ =J3’,2’ =7.2 Hz, 6H; 3 ꢃ 3’-H
.39 (qt, J3’,4’ =J3’,2’ =7.2 Hz, 6H; 3 ꢃ 3’-H ), 1.45–1.66 (m, 12H; 6 ꢃ 2’-
10,8 =1.3 Hz, each peak flanked by Sn isotope satellites as
2
),
2
=
1
H
2
4
1
1
2
), 2.07 (d,
J
doublets, JC-1’,117Sn =328.1, JC-1’,119Sn =343.3 Hz; 3 ꢃ C-1’), 10.76 (C-10),
12.67 (3 ꢃ C-4’), 12.70 (3 ꢃ C-4’), 18.78 (flanked by Sn isotope satellites
3
3
an incompletely resolved d, J10-H,117Sn ꢂ J10-H,119Sn ꢂ47 Hz, 3H; 10-H
3
), 2.09
4
3
3
(
d, J11,3 =1.5 Hz, each peak flanked by Sn isotope satellites as an incom-
as an incompletely resolved d, JC-9,117Sn ꢂ J
C-9,119Sn
ꢂ39 Hz; C-9), 26.28
3
3
3
pletely resolved d,
J
flanked by Sn isotope satellites as 2 interwoven doublets, J3-H,117Sn =63.4,
J
1-H,117Sn ꢂ J1-H,119Sn ꢂ47 Hz, 3H; 1-H
3
), 6.11 (dd, J6,7
=
(flanked by Sn isotope satellites as 2 interwoven doublets, J 117 =52.9,
C-3’, Sn
4
3
6,5 =10.5 Hz, 1H; 6-H), 6.37 (dd, J3,4 =9.9 Hz,
J
3,1 =1.8, each peak
JC-3’,119Sn =55.3 Hz; 3 ꢃ C-3’), 26.99 (flanked by Sn isotope satellites as 2
3
3
3
interwoven doublets, JC-3’,117Sn =53.1, JC-3’,119Sn =55.5 Hz; 3 ꢃ C-3’), 28.10
Chem. Eur. J. 2011, 17, 6469 – 6483
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6481

R. Brꢁckner et al.
2
(
J
flanked by Sn isotope satellites as an incompletely resolved d, JC-2’,117Sn
ꢂ
2
C-2’,119Sn ꢂ21 Hz; 3 ꢃ C-2’), 28.18 (flanked by Sn isotope satellites as an
[1] a) Metal-Catalyzed Cross-Coupling Reactions, 2nd ed. (Eds.: A. de
Meijere, F. Diederich), Wiley-VCH, Weinheim, 2004; b) Various au-
thors in: Handbook of Organopalladium Chemistry for Organic Syn-
thesis (Eds.: E. Negishi, A. de Meijere), Wiley-VCH, Weinheim,
2002, pp. 215–994.
[2] a) J. K. Stille, Angew. Chem. 1986, 98, 504–519; Angew. Chem. Int.
Ed. Engl. 1986, 25, 508–524; b) V. Farina, G. P. Roth in Advances in
Metal-Organic Chemistry, Vol. 5 (Ed.: L. S. Liebeskind), JAI Press,
Greenwich, 1996, pp. 1–53; c) V. Farina, V. Krishnamurthy, W. J.
Scott, Org. React. 1997, 50, 1–652; d) M. Kosugi, K. Fugami in
Handbook of Organopalladium Chemistry for Organic Synthesis
2
2
incompletely resolved d, JC-2’,117Sn ꢂ JC-2’,119Sn ꢂ20 Hz; 3 ꢃ C-2’), 122.81 (C-
6
), 123.01 (C-5), 124.88 (C-4), 127.84 (C-1), 133.19 (flanked by Sn isotope
2
2
satellites as an incompletely resolved d,
1
an incompletely resolved d,
J
C-7,117Sn ꢂ JC-7,119Sn ꢂ31 Hz; C-7),
36.36 (C-3), 146.05 (C-8), 149.90 ppm (flanked by Sn isotope satellites as
2
2
J
C-2,117Sn ꢂ JC-2,119Sn ꢂ11 Hz; C-2); IR (film):
n˜ =3025, 2955, 2925, 2870, 2850, 1560, 1465, 1420, 1375, 1340, 1295, 1075,
ꢀ1
9
95, 940, 870, 735, 710, 690, 665, 610, 595 cm ; HRMS (Cl, 120 eV):
+
calcd for C34
H
66Sn
2
: 712.32026 [M ]; found: 712.32260 (+3.3 ppm).
1E,3E,5Z,7E,9E)-1,10-Bis(tributylstannyl)deca-1,3,5,7,9-pentaene
mono-Z-29): Following the general procedure, mono-Z-29 was prepared
(
(
(
Eds.: E. Negishi, A. de Meijere), Wiley-VCH, Weinheim, 2002,
pp. 263–284; e) P. Espinet, A. M. Echavarren, Angew. Chem. 2004,
16, 4808–4839; Angew. Chem. Int. Ed. 2004, 43, 4704–4734;
from aldehyde 30 (100 mg, 0.265 mmol), benzothiazolylsulfone 10
1
f) T. N. Mitchell in Metal-Catalyzed Cross-Coupling Reactions, 2nd
ed. (Eds.: A. de Meijere, F. Diederich), Wiley-VCH, Weinheim,
2
004, pp. 125–162; g) M. V. N. De Souza, Curr. Org. Synth. 2006, 3,
3
13–326.
(
196 mg, 0.353 mmol, 1.2 equiv), and KHMDS (1.05 equiv). Flash chro-
[
3] a) K. C. Nicolaou, T. K. Chakraborty, A. D. Piscopio, N. Minowa, P.
Bertinato, J. Am. Chem. Soc. 1993, 115, 4419–4420; b) K. C. Nico-
laou, A. D. Piscopio, P. Bertinato, T. K. Chakraborty, N. Minowa, K.
Koide, Chem. Eur. J. 1995, 1, 318–333; c) C. E. Masse, M. Yang, J.
Solomon, J. S. Panek, J. Am. Chem. Soc. 1998, 120, 4123–4134; for a
conceptionally equivalent ring-closing biscoupling of Z-1,2-bis(tri-
methylstannyl)ethene, see: d) M. D. Shair, T. Y. Yoon, S. J. Danishef-
sky, J. Org. Chem. 1992, 57, 3755–3757; e) M. D. Shair, T. Y. Yoon,
K. K. Mosny, T. C. Chou, S. J. Danishefsky, J. Am. Chem. Soc. 1996,
[
26]
matography on deactivated Al
v), fractions 2 and 3) provided mono-Z-29 as a colorless oil (92.3 mg,
2 3 3
O (5ꢃ2 cm, cyclohexane/NEt 98:2 (v/
1
4
(
J
2
9%, mono-Z/all-Eꢃ96:4). H NMR (400.1 MHz, C
t, J4’,3’ =7.3, 18H; 6 ꢃ 4’-H ), 1.01 (m , 12H; 6 ꢃ 1’-H
), 1.51–1.72 (m, 12H; 6 ꢃ 2’-H
H; 5-H and 6-H), 6.26 (dd, J3,4 =J8,7 =14.5, J3,2 =J8,9 =10.1 Hz, 2H; 3-H
and 8-H), 6.45 (d, J1,2 =J10,9 =18.7 Hz, each peak flanked by Sn isotope
6
D
6
/C
), 1.38 (qt, J3’,4’
), 6.02 (m , d,
6 5
D H): d=0.92
3
c
2
=
3’,2’ =7.3 Hz, 12H; 6 ꢃ 3’-H
2
2
c
2
2
2
satellites as an incompletely resolved d,
J
1-H,117Sn ꢂ J1-H,119Sn ꢂ J10-H,117Sn ꢂ
2
J
10-H,119Sn ꢂ69 Hz, 2H; 1-H, 10-H), 6.68 (m
c
, 2H; 4-H, 5-H), 6.84 ppm (dd,
1
18, 9509–9525.
J
2,1 =J9,10 =18.6, J2,3 =J9,8 =10.2 Hz, each peak flanked by Sn isotope satel-
[
4] a) D. A. Siesel, S. W. Staley, Tetrahedron Lett. 1993, 34, 3679–3682;
b) D. A. Siesel, S. W. Staley, J. Org. Chem. 1993, 58, 7870–7875;
c) A. M. Echavarren, M. Pꢄrez, A. M. CastaÇo, J. M. Cuerva, J. Org.
Chem. 1994, 59, 4179–4185; d) G. Macdonald, L. Alcaraz, X. Wei,
N. J. Lewis, R. J. K. Taylor, Tetrahedron 1998, 54, 9823–9836;
e) D. L. Andersen, T. G. Back, L. Janzen, K. Michalak, R. P. Pharis,
G. C. J. Sung, J. Org. Chem. 2001, 66, 7129–7141; f) M. J. Frampton,
H. Akdas, A. R. Cowley, J. E. Rogers, J. E. Slagle, P. A. Fleitz, M.
Drobizhev, A. Rebane, H. L. Anderson, Org. Lett. 2005, 7, 5365–
3
3
3
3
lites as an incompletely resolved d, J2-H,117Sn ꢂ J2-H,119Sn ꢂ J9-H,117Sn ꢂ J9-H,119Sn
1
3
ꢂ58 Hz, 2 H; 2-H, 9-H); C NMR (100.6 MHz, C
6 6 6 6
D /C D ): d=9.90
1
(
3
C-1’,117Sn
flanked by Sn isotope satellites as 2 interwoven doublets, J =
28.4, JC-1’,119Sn =343.8 Hz; 6 ꢃ C-1’), 13.91 (6 ꢃ C-4’), 27.70 (flanked by
1
3
3
Sn isotope satellites as 2 interwoven doublets,
5
pletely resolved d,
7
C-3’,119Sn
JC-3’,117Sn =52.9, J =
4.8 Hz; 6 ꢃ C-3’), 29.57 (flanked by Sn isotope satellites as an incom-
2
2
J
C-2’,117Sn ꢂ JC-2’,119Sn ꢂ21 Hz; 6 ꢃ C-2’), 127.81 (C-4, C-
), 130.67 (C-5, C-6), 135.83 (flanked by Sn isotope satellites as 2 inter-
1
1
1
1
woven doublets,
J
C-1,117Sn = JC-10,117Sn =367.2,
J
C-1,119Sn = JC-10,119Sn =382.4 Hz;
5
368; g) a related mono-coupling was described by: P. M. Pihko,
C-1, C-10), 137.00 (flanked by Sn isotope satellites as 2 interwoven dou-
blets,
1
d,
1
(
3
3
3
3
A. M. P. Koskinen, Synlett 1999, 1966–1968.
5] a) A. Kiehl, A. Eberhardt, K. Mꢁllen, Liebigs Ann. 1995, 223–230;
b) D. Nozawa, H. Takikawa, K. Mori, J. Chem. Soc. Perkin Trans. 1
J
C-3,117Sn = JC-8,117Sn =69.5,
J
C-3,119Sn = JC-8,119Sn =75.3 Hz; C-3, C-8),
[
47.73 ppm (flanked by Sn isotope satellites as an incompletely resolved
2
2
2
2
J
C-2,117Sn ꢂ JC-9,117Sn ꢂ JC-2,119Sn ꢂ JC-9,119Sn ꢂ9 Hz; C-2, C-6); HRMS (CI,
+
2000, 2043–2046; by refining this kind of approach, E,E-BnMe Siꢀ
20 eV): calcd for
C
34
H
64Sn
2
:
710.30461 [M ]; found: 710.30590
2
CH=CHꢀCH=CHꢀSiMe
(OH) and E,E-(thienyl)Me
SiꢀCH=CHꢀ
+1.8 ppm).
2
2
CH=CHꢀSiMe
2
(OH) were prepared (S. E. Denmark, S. A. Tymon-
(
1E,3E,5Z,7E,9E)-3,8-Dimethyl-1,10-bis(tributylstannyl)deca-1,3,5,7,9-
ko, J. Am. Chem. Soc. 2005, 127, 8004–8005) and the former com-
pound was subjected to sequential Hiyama couplings (S. E. Den-
mark, S. Fujimori, J. Am. Chem. Soc. 2005, 127, 8971–8973).
pentaene (mono-Z-32): Following the general procedure, mono-Z-32
was prepared from aldehyde 27 (89.0 mg, 0.231 mmol), benzothiazolylsul-
fone 33 (147.3 mg, 0.259 mmol, 1.12 equiv), and KHDMS (1.12 equiv).
[
26]
[6] A. Sorg, R. Brꢁckner, Angew. Chem. 2004, 116, 4623–4626; Angew.
Chem. Int. Ed. 2004, 43, 4523–4526.
[7] R. Brꢁckner, K. Siegel, A. Sorg in Strategies and Tactics in Organic
Synthesis, Vol. 5 (Ed.: M. Harmata), Elsevier, Amsterdam, 2004,
pp. 437–473.
Flash chromatography on deactivated Al
NEt 100:1 (v/v), fractions 3 and 4), provided mono-Z-32 as a yellow oil
142.2 mg, 63% (83%), mono-Z/all-E=94:6; see refs [10] and [20] for
2 3
O (5ꢃ2.5 cm, cyclohexane/
3
[
10]
(
the definitive stereochemical assignment and ref. [10] for analytical data.
[
[
8] A. Sorg, K. Siegel, R. Brꢁckner, Chem. Eur. J. 2005, 11, 1610–1624.
9] J. Burghart, R. Brꢁckner, Angew. Chem. 2008, 120, 7777–7782;
Angew. Chem. Int. Ed. 2008, 47, 7664–7668.
[
[
10] B. Vaz, R. Alvarez, A. R. de Lera, J. Org. Chem. 2002, 67, 5040–
043.
11] a) Use of E,E-1-(tributylstannyl)-6-(trimethylsilyl)hexa-1,3-dien-5-
yne as a synthetic equivalent of E,E,E-1-[chlorobis(cyclopentadie-
nyl)zirconio]-6-(tributylstannyl)hexa-1,3,5-triene or E,E,E-1-[chloro-
bis(cyclopentadienyl)zirconio]-2-methyl-6-(tributylstannyl)hexa-
5
Acknowledgements
We are indebted for financial support from the European Graduate Col-
lege “Catalysts and Catalytic Reactions for Organic Synthesis” of the
German Research Foundation (DFG) and to Juliane Huber for technical
assistance.
1
1
,3,5-triene: B. H. Lipshutz, C. Lindsley, J. Am. Chem. Soc. 1997,
19, 4555–4556; b) use of E,E- or Z,E-2-(tributylstannyl)-7-(trime-
thylsilyl)hepta-2,4-dien-6-yne as synthetic equivalents of E,E,E- and
E,E,Z-1-(dialkylalumino)-2,6-dimethyl-6-(tributylstannyl)hepta-
1
,3,5-triene: B. H. Lipshutz, G. C. Closowski, W. Chrisman, D. W.
Chung, D. B. Ball, J. Howell, Org. Lett. 2005, 7, 4561–4564.
6482
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 6469 – 6483

1
,w-Bis(tributylstannylated) Conjugated Trienes
FULL PAPER
[
[
[
[
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(
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[
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U
G
R
N
U
G
4
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[
2
a
(
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2
2 2 3
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[
[
[
[
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[
[
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[
[
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2
(
Received: June 9, 2010
Published online: April 21, 2011
Chem. Eur. J. 2011, 17, 6469 – 6483
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6483