Nickel-Catalyzed Homocoupling of (Z)-β-Iodoenol Esters: Stereoselective Access to (Z, Z)-Buta-1,3-diene-1,4-diyl Diesters

Article abstract of DOI:10.1055/s-0037-1610709

A straightforward and broad-scope procedure to obtain symmetrically substituted buta-1,3-diene-1,4-diyl diesters, based on the homocoupling of the corresponding (Z)-β-iodoenol esters, is presented. It involves the use of a catalytic system composed of [NiCl ₂ (PPh ₃) ₂ ] (10 molpercent), NaI (10 molpercent), and excess of Zn dust. The reactions proceed in THF at room temperature with exquisite preservation of the stereochemistry of the C=C bond of the starting iodoolefins, thus leading to the final dienes as the corresponding Z, Z -stereoisomers exclusively.

Full text of DOI:10.1055/s-0037-1610709

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2019, 51, A–J
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J. Francos, V. Cadierno
Paper
Synthesis
Nickel-Catalyzed Homocoupling of (Z)--Iodoenol Esters:
Stereoselective Access to (Z,Z)-Buta-1,3-diene-1,4-diyl Diesters
Javier Francos
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Stereoselective homocoupling of (Z)-b-iodoenol esters
R2
R1
Victorio Cadierno*
[NiCl2(PPh3)2] (10 mol%)
I
O
O
O
R1
R2
NaI (10 mol%), Zn (1.6 equiv)
THF, r.t., 16 h
Laboratorio de Compuestos Organometálicos y Catálisis (Unidad Aso-
ciada al CSIC), Centro de Innovación en Química Avanzada (ORFEO-
CINQA), Departamento de Química Orgánica e Inorgánica, IUQOEM,
Universidad de Oviedo, Julián Clavería 8, 33006 Oviedo, Spain
vcm@uniovi.es
R2
R1
O
O
O
R1 = alkyl or aryl group
R2 = alkyl, aryl, heteroaryl or alkenyl group
33 examples
40–89% yield
Dedicated to Prof. Pablo Espinet on the occasion of his 70th birthday
Received: 20.02.2019
Accepted after revision: 05.04.2019
Published online: 25.04.2019
Among the different methods currently available for the
synthesis of enol esters A,3 the addition of carboxylic acids
to alkynes catalyzed by transition metal complexes is prob-
ably the most versatile and appealing one, due to its com-
plete atom economy and substrate availability (Scheme
1).4,5 In this regard, in the context of our studies on this type
of hydrocarboxylation processes,6 we recently developed a
wide scope procedure for the synthesis of (Z)--iodoenol
esters 1 through the regio- and stereoselective intermolec-
ular addition of carboxylic acids to iodoalkynes catalyzed
by gold(I) (Scheme 2).6d,f,g Compounds 1 proved to be useful
starting materials for the preparation of a large variety of
stereochemically defined -arylvinyl esters 26d,g and enynyl
esters 36f via Suzuki and Sonogashira cross-coupling reac-
tions, respectively (Scheme 2). In addition, in collaboration
with Pizzano’s group (IIQ-Seville), we also studied the
asymmetric hydrogenation of 2 using Rh catalysts, which
allowed the access to the corresponding chiral homoben-
zylic esters with high enantioselectivity levels.6d,g
DOI: 10.1055/s-0037-1610709; Art ID: ss-2019-z0113-op
Abstract A straightforward and broad-scope procedure to obtain
symmetrically substituted buta-1,3-diene-1,4-diyl diesters, based on
the homocoupling of the corresponding (Z)--iodoenol esters, is pre-
sented. It involves the use of
a catalytic system composed of
[NiCl2(PPh3)2] (10 mol%), NaI (10 mol%), and excess of Zn dust. The re-
actions proceed in THF at room temperature with exquisite preserva-
tion of the stereochemistry of the C=C bond of the starting iodoolefins,
thus leading to the final dienes as the corresponding Z,Z-stereoisomers
exclusively.
Key words homocoupling reactions, nickel, iodoalkenes, buta-1,3-
dienes, enol esters, diesters
Enol esters A are an important class of compounds
widely employed as substrates and intermediates in organic
chemistry.1 In particular, much attention has been devoted
to the asymmetric hydrogenation of these molecules, since
the resulting saturated esters B can be easily converted into
synthetically relevant chiral alcohols C through a trivial
deacylation process (Scheme 1).2
[AuCl(PPh3)] (5 mol%)
I
R1
I
AgPF6 (5 mol%)
+
toluene, r.t.
OC(O)R2
R2CO2H
R1
1
R2
asymmetric
hydrogenation
R2
R1
R3
(1.3 equiv)
[Pd(PPh3)4] (5 mol%)
CuI (10 mol%), Et3N (10 equiv)
1,4-dioxane, r.t.
OC(O)R3
ArB(OH)2 (1.5 equiv)
[Pd(PPh3)4] (5 mol%)
NaOH (2 equiv)
OC(O)R3
R1
B
A
toluene, 80 °C
deprotection
hydrocarboxylation
R3
R2
R1
Ar
R1
R2
+
OC(O)R2
R1
R3CO2H
OC(O)R2
R1
OH
C
2
3
R1 = alkyl, aryl; R2 = alkyl, aryl, heteroaryl, alkenyl; R3 = alkyl, aryl, alkenyl
Scheme 1 Synthesis and asymmetric hydrogenation of enol esters
Scheme 2 Synthesis and palladium-catalyzed C–C couplings of (Z)--
iodoenol esters 1
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

B
J. Francos, V. Cadierno
Paper
Synthesis
In this work, the synthetic utility of the (Z)--iodoenol
esters 1 is further demonstrated with their successful in-
volvement in homocoupling reactions to generate symmet-
rically substituted (Z,Z)-buta-1,3-diene-1,4-diyl diesters 4
(Figure 1).7 This type of conjugated dienes are scarcely rep-
resented in the literature. In fact, to the best of our knowl-
edge, only five examples are currently known, with only
one of them featuring the same stereochemistry as com-
pounds 4 (Figure 1).8
[PdCl2(PPh3)2] (5 mol%)
PPh3 (10 mol%)
B2pin2 (0.5 equiv)
CsF (3.5 equiv)
OAc
( )n
I
( )n
THF, 70 °C, overnight
(25–31% yield)
( )n
OAc
OAc
n = 2 (4a), 3 (4b)
n = 2 (1a), 3 (1b)
Scheme 4 Pd-catalyzed homocoupling of the (Z)--iodoenol esters
1a,b. B2pin2 = bis(pinacolato)diboron.
HO
OC(O)R2
R1
vent, temperature, time, and amounts of reagents) were un-
successful.
OAc
OH
OAc
Z
E
Z
R1
Z
Z
Z
Mes
Mes
The use of stoichiometric or catalytic amounts of zero-
valent nickel complexes for homocoupling reactions of alke-
nyl halides is well documented, and this methodology is the
one that led to the best results in the present case.13 Thus,
as shown in Table 1, the treatment of a THF solution of (Z)-
1-iodopent-1-en-2-yl acetate (1a) with 30 mol% of
[NiCl2(PPh3)2], in the presence of Zn powder (2 equiv) as the
reductant and Bu4NI (1 equiv) as an additive to assist the re-
duction of Ni(II) to Ni(0),13c,f for 16 hours resulted in the
clean formation of the desired diene 4a, which was isolated
in 67% yield after appropriate chromatographic workup (Ta-
ble 1, entry 1). Interestingly, the reaction gives 4a as the
corresponding Z,Z-isomer exclusively, indicating that Z → E
isomerization of the starting iodoolefin does not take place
along the process.13f Reduction of the nickel loading to 10
mol% led practically to the same result (entry 2), while the
use of only 5 mol% of [NiCl2(PPh3)2] resulted in a significant
decrease in the effectiveness of the process (entry 3). Addi-
tional experiments also revealed the need to include the
three components of the catalytic system for the reaction to
proceed efficiently (entries 4–6). On the other hand, as
shown in entry 7, the addition of extra PPh3 to the reaction
medium did not lead to significant changes in the yield of
4a.13c,f Alternative nickel sources, for example, NiCl2 and
[NiCl2(glyme)], were also explored and resulted less effec-
tive than [NiCl2(PPh3)2] (entries 8, 9). On the contrary, the
use of inorganic iodide sources instead of Bu4NI allowed to
improve the yield of 4a (entries 10, 11). In particular, the
best results were obtained with NaI, which led to 4a in
>80% yield even when only 10 mol% was added to the reac-
tion medium (entries 11–14). As shown in entry 14, under
these conditions, it was also possible to reduce the quantity
of Zn employed (82% yield). Finally, other solvents, such as
toluene or CH2Cl2, were also screened but resulted less ef-
fective (entries 15, 16 vs entry 14).
OC(O)R2
OAc
OAc
4
OAc
OBz
CN
Z
Z
E
E
E
E
AcO
BzO
AcO
CN
CO2Et
OAc
CN
CO2Et
CN
Figure 1 The generic structure of compounds 4 and that of related
buta-1,3-dienes reported in the literature
On the other hand, we would like also to stress that, as
we have very recently communicated employing a small
family of alkyl-substituted diacetates (Scheme 3), the asym-
metric hydrogenation of dienes 4 can open new routes for
the synthesis of C2 symmetric 1,4-diols, key building blocks
in the preparation of a broad range of chiral heterocycles.9
Herein, a full report on the preparation of (Z,Z)-buta-1,3-di-
ene-1,4-diyl diesters 4 is presented.
asymmetric
hydrogenation
OAc
Alk
OAc
Alk
Alk
Alk
OAc
OAc
deprotection
Alk
(10 examples)
OH
Alk
OH
Scheme 3 Access to C2 symmetric 1,4-diols from (Z,Z)-buta-1,3-diene-
1,4-diyl diacetates
Initial attempts to promote the homocoupling of the
(Z)--iodoenol esters 1 with copper(I) thiophene-2-carbox-
ylate (CuTC),10 a reagent with proven effectiveness in reduc-
tive homocoupling reactions of aryl, heteroaryl, and alkenyl
halides,11 failed. Thus, regardless of the stoichiometry, sol-
vent, and temperature employed, the starting iodoolefins
were recovered unchanged. Different palladium-based
methodologies described in the literature were also tested
with little success.12 Among them, only the one developed
by Eddarir and Rolando led to the desired 1,3-dienes.12b
However, as shown in Scheme 4 for the representative sub-
strates 1a,b, the yields were very low and all attempts to
improve them by changing the reaction parameters (sol-
With the optimized reaction conditions in hand (Table
1, entry 14), the scope of the process was next explored. In
this regard, the behavior of a series of (Z)--iodoenol ace-
tates 1b–o was first investigated (Scheme 5). Thus, as ob-
served for 1a, other iodoolefins containing alkyl and cy-
cloalkyl substituents 1b–h could be successfully converted
into the corresponding buta-1,3-diene-1,4-diyl diacetates
4b–h in high yields (71–89%). Good results were also ob-
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

C
J. Francos, V. Cadierno
Paper
Synthesis
Table 1 Nickel-Catalyzed Homocoupling of the (Z)--Iodoenol Acetate
1a: Optimization of the Reaction Conditionsa
homocoupling reactions proceeded with complete preser-
vation of the stereochemistry of the C=C bond of the start-
ing iodoolefins 1, leading to compounds 4 as the corre-
sponding Z,Z-stereoisomers exclusively. In this regard, the
1H and 13C NMR spectra confirmed the equivalence of the
two CH=CR(OAc) units of 4a–o, with singlet signals at  =
5.58–6.64 and  = 107.3–110.7 (=CH) and 146.9–154.0 (=C)
being characteristic fingerprints of the symmetrically sub-
stituted 1,3-dienic units (see details in the Experimental
Section). In addition, the molecular structure of (Z,Z)-1,4-
dicyclopentylbuta-1,3-diene-1,4-diyl diacetate (4g) was
also determined by X-ray diffraction analysis, for which
good quality crystals could be obtained by slow diffusion of
hexane into a saturated solution of the compound in ethyl
acetate.14 An ORTEP-type drawing of the molecule, along
with selected bonding parameters, is shown in Figure 2. The
C(3)–C(4) and C(4)–C(4a) bond lengths observed [1.330(2)
and 1.449(3) Å, respectively] fit well with those of the par-
ent unsubstituted 1,3-butadiene molecule (C=C = 1.341 Å
and C–C = 1.463 Å).15
[NiCl2(PPh3)2]/Zn
iodide salt
OAc
I
THF, r.t., 16 h
OAc
OAc
1a
4a
Entry [NiCl2(PPh3)2] (mol%) Iodide salt
Zn (equiv) Yield (%)b
1
30
10
5
Bu4NI (1 equiv)
Bu4NI (1 equiv)
Bu4NI (1 equiv)
–
2
67
65
33
27
0
2
2
3
2
4
10
10
–
2
5
Bu4NI (1 equiv)
Bu4NI (1 equiv)
Bu4NI (1 equiv)
Bu4NI (1 equiv)
Bu4NI (1 equiv)
KI (1 equiv)
–
6
2
0
7c
8d
9e
10
10
10
10
10
10
10
10
10
10
2
63
48
62
75
84
84
83
82
65
47
2
2
10
2
On the other hand, although all the reactions collected
in Scheme 5 were systematically carried out on a 1 mmol
scale, they can be scaled up without major problems. As a
representative example, a reaction conducted with (Z)-1-
iodooct-1-en-2-yl acetate (1d) on a 10 mmol scale (2.96 g)
allowed the preparation of 1.32 g (78% yield) of (Z,Z)-hexa-
deca-7,9-diene-7,10-diyl diacetate (4d).
11
12
13
14
15f
16g
NaI (1 equiv)
NaI (50 mol%)
NaI (10 mol%)
NaI (10 mol%)
NaI (10 mol%)
NaI (10 mol%)
2
2
2
1.6
1.6
1.6
Finally, in order to assess in more detail the scope of the
process, the homocoupling of a series of (Z)-1-iodohex-1-
en-2-yl esters 1p–ag, featuring different aliphatic, aromatic,
heteroaromatic, heterocyclic and ,-unsaturated substitu-
ents on the carboxylate unit, was explored under identical
experimental conditions (Scheme 6). To our delight, the
catalytic reaction proved to be broadly applicable, and the
novel 1,3-dienes 4p–ag could be synthesized with complete
stereoselectivity in moderate to good yields (40–89%).
Concerning the mechanism of the present homocou-
pling process, we assume that it proceeds through the reac-
tion pathway proposed by Takagi and co-workers (Scheme
a Reactions performed under argon atmosphere for 16 h employing 1
mmol of 1a and 5 mL of anhyd THF.
b Isolated yield after chromatographic workup is given.
c Reaction performed in the presence of free PPh3 (20 mol%).
d Reaction performed employing NiCl2 instead of [NiCl2(PPh3)2].
e Reaction performed employing [NiCl2(glyme)] instead of [NiCl2(PPh3)2].
f Reaction performed in toluene.
g Reaction performed in CH2Cl2.
tained employing substrates bearing phenyl-substituted al-
kyl groups (1i–k) and those generated by addition of acetic
acid to aromatic iodoalkynes (1l–o), the resulting dienes
4i–o being isolated in 68–81% yield. Remarkably, all these
[NiCl2(PPh3)2] (10 mol%)
NaI (10 mol%), Zn (1.6 equiv)
OAc
I
R
R
THF, r.t., 16 h
(57–89% yield)
R
OAc
OAc
4a–o
1a–o
OAc
( )n
OAc
n = 2 (4a; 82%)
n = 3 (4b; 89%)
n = 4 (4c; 85%)
n = 5 (4d; 80%)
OAc
( )n
n = 1 (4f; 77%)
n = 3 (4g; 81%)
n = 4 (4h; 71%)
( )
n
( )n
OAc
OAc
OAc
Ph
4e (75%)
Ar = Ph (4l; 78%)
OAc
( )n
OAc
n = 1 (4i; 77%)
n = 2 (4j; 74%)
n = 3 (4k; 78%)
Ar = 4-C6H4Me (4m; 77%)
Ar = 4-C6H4F (4n; 68%)
Ar = 3-C6H4OMe (4o; 81%)
Ar
( )
Ph
n
Ar
OAc
OAc
Scheme 5 Nickel-catalyzed homocoupling of (Z)--iodoenol acetates 1a–o. Isolated yields after column chromatography are given.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

D
J. Francos, V. Cadierno
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Synthesis
final diene product. In this disproportionation step,
[NiI2(PPh3)2] is also generated and reduced by the Zn pow-
der to ensure the catalytic cycle.
R1
Zn/I–
[NiCl2(PPh3)2]
ZnX2
R1
R2(O)CO
R2(O)CO
I
[Ni(PPh3)2]
[Ni(PPh3)2]
I
Zn/I–
ZnI2
OC(O)R2
R1
D
R1
OC(O)R2
[NiI2(PPh3)2]
R1
R1
R2(O)CO
R1
Figure 2 ORTEP-type view of the structure of diene 4g showing the
crystallographic labeling scheme. Hydrogen atoms, except those on
C(4) and C(4a), have been omitted for clarity. The atoms labeled with ‘a’
are generated by symmetry. Thermal ellipsoids are drawn at 30% proba-
bility level. Selected bond lengths (Å): C(1)–O(1) 1.365(2), C(1)–O(2)
1.199(2), C(1)–C(2) 1.488(2), C(3)–O(1) 1.410(2), C(3)–C(4) 1.330(2),
C(3)–C(5) 1.493(2), C(4)–C(4a) 1.449(3). Selected bond angles (°):
O(1)–C(1)–O(2) 122.7(2), O(1)–C(1)–C(2) 110.7(2), O(2)–C(1)-–(2)
126.6(2), C(1)–O(1)–C(3) 117.9(1), O(1)–C(3)–C(4) 119.3(1), O(1)–
C(3)–C(5) 114.3(1), C(3)–C(5)–C(6) 114.5(1), C(3)–C(5)–C(9) 116.1(1),
C(3)–C(4)–C(4a) 125.3(2).
[Ni(PPh3)2]
R2(O)CO
R1
[Ni(PPh3)2]
I
R2(O)CO
[Ni(PPh3)2]
R2(O)CO
I
E
Scheme 7 Proposed mechanism for the homocoupling process
Regarding the stereoselectivity of the process, as dis-
cussed by Takagi and co-workers,16 both the oxidative addi-
tion and reductive elimination steps are known to proceed
with retention of configuration of the alkenyl group. The
exclusive formation of the Z,Z-stereoisomers implies that,
unlike what is usually observed with other alkenyl ha-
lides,13,16 no isomerization of the C=C bond takes place in
the present case at the disproportionation stage. Although
we have no conclusive explanation for this, we suspect that
7).16 It would involve the oxidative addition of the -iodo-
enol ester to in situ formed Ni(0)-phosphine species gener-
ated by reduction of [NiCl2(PPh3)2] with Zn, a process that is
facilitated by the NaI present in the reaction medium. Sub-
sequent disproportionation of intermediate D thus formed,
would generate the corresponding bis(alkenyl)-Ni(II) deriv-
ative E, which undergoes reductive elimination to form the
[NiCl2(PPh3)2] (10 mol%)
NaI (10 mol%), Zn (1.6 equiv)
OC(O)R
( )3
I
( )3
THF, r.t., 16 h
(40–89% yield)
( )3
OC(O)R
OC(O)R
1p–ag
4p–ag
( )n
O
tBu
iPr
R
O
R = Me (4p; 79%)
O
O
O
O
O
O
R = n-C5H11 (4q; 82%)
R = n-C6H13 (4r; 82%)
R = CH2Br (4s; 75%)
R = CH2-c-C5H9 (4t; 54%)
R = Ph (4u; 77%)
( )3
( )3
( )3
( )3
( )3
( )3
( )3
( )3
O
O
O
O
4w (43%)
4v (89%)
O
O
R
O
O
n = 1 (4x; 84%)
n = 4 (4y; 84%)
tBu
iPr
( )n
Ph
S
O
Ar
O
O
Ar = Ph (4z; 55%)
Ar = 4-C6H4OMe (4aa; 53%)
Ar = 4-C6H4F (4ab; 61%)
O
O
O
O
O
O
( )3
Ar
( )3
( )3
( )3
( )3
( )3
( )3
( )3
O
O
Ar = 4-C6H4CH=CH2 (4ac; 64%)
Ar = 3-C6H4Me (4ad; 58%)
O
O
O
O
O
O
4ae (43%)
4af (40%)
4ag (44%)
S
O
Ph
Scheme 6 Nickel-catalyzed homocoupling of (Z)--iodoenol esters 1: Scope of the process concerning the nature of the carboxylate group. Isolated
yields after column chromatography are given.
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E
J. Francos, V. Cadierno
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Synthesis
a potential interaction/coordination of the ester groups to
Ni could be responsible for the high stereoselectivity ob-
served.
HRMS (ESI): m/z [M + Na]+ calcd for C14H22O4Na: 277.1410; found:
277.1406.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Diacetate (4b)
In summary, we have developed a general and inexpen-
sive protocol for the preparation of buta-1,3-diene-1,4-diyl
diesters, a family of underrepresented conjugated dienes,
from readily accessible (Z)--iodoenol esters. The catalytic
homocoupling of the latter proceeded cleanly, and under
mild conditions, in the presence of zero-valent nickel spe-
cies generated in situ by combining [NiCl2(PPh3)2], NaI, and
Zn dust. Exquisite preservation of the stereochemistry of
the C=C bond of the starting iodoolefins was observed in all
the cases, and the reactions lead to the 1,3-diene products
in a completely stereospecific manner with isolated yields
ranging from 40% to 89%.
White solid; yield: 0.126 g (0.446 mmol, 89%); mp 57–59 °C.
IR (KBr): 2954, 2870, 1760, 1647, 1430, 1371, 1200, 1099, 1024, 933,
878, 831, 785, 735, 692, 611, 573, 504, 490 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 5.64 (s, 2 H, =CH), 2.26 (t, J = 7.2 Hz, 4
H, CH2), 2.19 (s, 6 H, CH3), 1.44–1.40 (m, 4 H, CH2), 1.35–1.31 (m, 4 H,
CH2), 0.90 (t, J = 7.2 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 168.6, 149.9, 109.0, 33.3, 28.7, 22.1,
20.8, 13.8.
HRMS (ESI): m/z [M + H]+ calcd for C16H27O4: 283.1904; found:
283.1908.
(Z,Z)-Tetradeca-6,8-diene-6,9-diyl Diacetate (4c)
White solid; yield: 0.132 g (0.425 mmol, 85%); mp 60–62 °C.
IR (KBr): 2959, 2873, 1745, 1646, 1466, 1428, 1374, 1201, 1102, 1046,
All reactions were performed under an argon atmosphere using stan-
dard Schlenk-type techniques. Solvents were distilled under argon
with Na-benzophenone-ketyl (for Et2O and THF) or Na (for hexanes).
The (Z)--iodoenol esters 1 were synthesized by hydrocarboxylation
of the corresponding iodoalkyne as previously described by us
(Scheme 2).6f Characterization data for compounds 1o–y,aa–ag, not
previously reported, have been included in the Supporting Informa-
tion. [NiCl2(PPh3)2] was prepared by following the method described
in the literature.17 All other reagents were purchased from commer-
cial suppliers and used as received. IR spectra were recorded on a
PerkinElmer 1720-XFT spectrophotometer. NMR spectra were ob-
tained on Bruker DPX-300 or AV-400 spectrometer. 13C{1H} and 1H
chemical shifts were referenced to the residual signal of deuterated
solvent. All data are reported in ppm downfield from (CH3)4Si. For
19F{1H} NMR spectra, the chemical shifts were referenced to the CFCl3
standard. All NMR measurements were carried out at 25 °C. HRMS
data were obtained on a ESI-q-TOF Bruker Impact II mass spectrome-
ter. For column chromatography, Merck silica gel 60 (230–400 mesh)
was employed.
1015, 934, 880, 853, 815, 730, 610, 576, 489 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.65 (s, 2 H, =CH), 2.27 (t, J = 7.2 Hz, 4
H, CH2), 2.21 (s, 6 H, CH3), 1.48–1.43 (m, 4 H, CH2), 1.32–1.29 (m, 8 H,
CH2), 0.90 (t, J = 7.2 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 168.6, 149.9, 109.1, 33.6, 31.2, 26.3,
22.4, 20.8, 14.0.
HRMS (ESI): m/z [M + Na]+ calcd for C18H30O4Na: 333.2036; found:
333.2034.
(Z,Z)-Hexadeca-7,9-diene-7,10-diyl Diacetate (4d)
White solid; yield: 0.135 g (0.399 mmol, 80%); mp 48–51 °C.
IR (KBr): 2925, 2857, 1754, 1643, 1438, 1374, 1201, 1130, 1018, 933,
871, 809, 722, 622, 578, 554, 465 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 5.63 (s, 2 H, =CH), 2.25 (t, J = 7.6 Hz, 4
H, CH2), 2.19 (s, 6 H, CH3), 1.44–1.41 (m, 4 H, CH2), 1.27 (br, 12 H, CH2),
0.88 (t, J = 6.0 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 168.6, 149.9, 109.1, 33.6, 31.6, 28.7,
26.6, 22.5, 20.8, 14.0.
(Z,Z)-Buta-1,3-diene-1,4-diyl Diesters 4; General Procedure
HRMS (ESI): m/z [M + Na]+ calcd for C20H34O4Na: 361.2349; found:
361.2351.
A suspension of [NiCl2(PPh3)2] (0.065 g, 0.1 mmol), NaI (0.015 g, 0.1
mmol), and Zn dust (0.105 g, 1.6 mmol) in THF (5 mL) was stirred at
r.t. for 30 min. After this time, a solution of the corresponding (Z)--
iodoenol ester 1 (1 mmol) in THF (2 mL) was added and the resulting
mixture was stirred further at r.t. for 16 h. The solvent was then re-
moved under reduced pressure, and the crude reaction mixture di-
rectly purified by flash column chromatography over silica gel, using
hexanes/Et2O (10:1) as eluent, to provide the respective desired prod-
uct 4.
(Z,Z)-2,11-Dimethyldodeca-5,7-diene-5,8-diyl Diacetate (4e)
White solid; yield: 0.116 g (0.373 mmol, 75%); mp 65–67 °C.
IR (KBr): 2952, 2864, 1747, 1650, 1470, 1441, 1372, 1261, 1216, 1131,
1098, 1017, 935, 906, 856, 810, 767, 671, 614, 590, 543, 478 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.64 (s, 2 H, =CH), 2.27 (t, J = 7.5 Hz, 4
H, CH2), 2.21 (s, 6 H, CH3), 1.59–1.53 (m, 2 H, CH), 1.38–1.30 (m, 4 H,
CH2), 0.89 (d, J = 6.6 Hz, 12 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 168.6, 150.1, 108.9, 35.6, 31.6, 27.6,
22.4, 20.8.
(Z,Z)-Deca-4,6-diene-4,7-diyl Diacetate (4a)
White solid; yield: 0.104 g (0.409 mmol, 82%); mp 61–63 °C.
IR (KBr): 2960, 2872, 1750, 1645, 1435, 1376, 1260, 1200, 1112, 1038,
HRMS (ESI): m/z [M + Na]+ calcd for C18H30O4Na: 333.2036; found:
333.2040.
1010, 942, 820, 721, 610, 577, 541, 500, 461 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.61 (s, 2 H, =CH), 2.21 (t, J = 7.5 Hz, 4
H, CH2), 2.15 (s, 6 H, CH3), 1.53–1.41 (m, 4 H, CH2), 0.88 (t, J = 7.2 Hz, 6
H, CH3).
13C NMR (CDCl3, 75 MHz):  = 168.5, 149.6, 109.2, 35.6, 20.7, 19.9,
13.5.
(Z,Z)-1,4-Dicyclopropylbuta-1,3-diene-1,4-diyl Diacetate (4f)
White solid; yield: 0.096 g (0.383 mmol, 77%); mp 53–55 °C.
IR (KBr): 3095, 3019, 2929, 1751, 1635, 1559, 1436, 1374, 1261, 1194,
1156, 1043, 1008, 932, 885, 802, 656, 613, 574, 502 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

F
J. Francos, V. Cadierno
Paper
Synthesis
1H NMR (CDCl3, 300 MHz):  = 5.66 (s, 2 H, =CH), 2.21 (s, 6 H, CH3),
1.65–1.56 (m, 2 H, CH), 0.72–0.66 (m, 4 H, CH2), 0.61–0.58 (m, 4 H,
CH2).
13C NMR (CDCl3, 75 MHz):  = 168.6, 149.8, 108.3, 20.6, 14.3, 5.7.
HRMS (ESI): m/z [M + Na]+ calcd for C14H18O4Na: 273.1097; found:
(Z,Z)-1,10-Diphenyldeca-4,6-diene-4,7-diyl Diacetate (4k)
White solid; yield: 0.158 g (0.388 mmol, 78%); mp 107–109 °C.
IR (KBr): 3023, 2944, 2860, 1746, 1644, 1602, 1498, 1462, 1369, 1204,
1121, 1018, 932, 882, 827, 798, 752, 701, 614, 576, 535, 498, 461 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 7.35–7.20 (m, 10 H, ArH), 5.70 (t, J = 4.3
Hz, 2 H, =CH), 2.67 (t, J = 7.4 Hz, 4 H, CH2), 2.38–2.35 (m, 4 H, CH2),
2.22 (s, 6 H, CH3), 1.85–1.82 (m, 4 H, CH2).
273.1100.
(Z,Z)-1,4-Dicyclopentylbuta-1,3-diene-1,4-diyl Diacetate (4g)
White solid; yield: 0.124 g (0.405 mmol, 81%); mp 60–62 °C.
IR (KBr): 2961, 2870, 1751, 1638, 1436, 1376, 1207, 1137, 1017, 950,
13C NMR (CDCl3, 75 MHz):  = 168.6, 149.4, 141.8, 128.5, 128.4, 125.9,
109.6, 35.1, 33.2, 28.2, 20.8.
HRMS (ESI): m/z [M + Na]+ calcd for C26H30O4Na: 429.2036; found:
429.2040.
890, 857, 822, 720, 640, 571, 538, 432 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.64 (s, 2 H, =CH), 2.75–2.64 (m, 2 H,
CH), 2.20 (s, 6 H, CH3), 1.81 (br, 4 H, CH2), 1.66–1.46 (m, 12 H, CH2).
(Z,Z)-1,4-Diphenylbuta-1,3-diene-1,4-diyl Diacetate (4l)
13C NMR (CDCl3, 75 MHz):  = 168.7, 152.4, 107.8, 44.1, 30.5, 24.8,
Pale yellow solid; yield: 0.126 g (0.391 mmol, 78%); mp 170–172 °C.
20.7.
IR (KBr): 3079, 2929, 1757, 1610, 1574, 1492, 1447, 1367, 1200, 1185,
1040, 1025, 860, 755, 687, 626, 569, 518, 442 cm–1
.
HRMS (ESI): m/z [M + Na]+ calcd for C18H26O4Na: 329.1723; found:
1H NMR (CDCl3, 300 MHz):  = 7.50–7.36 (m, 10 H, ArH), 6.59 (s, 2 H,
329.1726.
=CH), 2.38 (s, 6 H, CH3).
(Z,Z)-1,4-Dicyclohexylbuta-1,3-diene-1,4-diyl Diacetate (4h)
White solid; yield: 0.119 g (0.356 mmol, 71%); mp 57–59 °C.
IR (KBr): 2950, 2873, 1753, 1635, 1440, 1377, 1215, 1200, 1140, 1009,
13C NMR (CDCl3, 75 MHz):  = 168.6, 148.1, 134.6, 128.9, 128.7, 124.7,
110.4, 20.7.
HRMS (ESI): m/z [M + Na]+ calcd for C20H18O4Na: 345.1097; found:
345.1098.
964, 901, 845, 811, 743, 654, 592, 555, 449 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.58 (s, 2 H, =CH), 2.22 (s, 6 H, CH3),
2.19–2.14 (m, 2 H, CH), 1.89–1.66 (m, 10 H, CH2), 1.32–1.08 (m, 10 H,
CH2).
(Z,Z)-1,4-Bis(4-methylphenyl)buta-1,3-diene-1,4-diyl Diacetate
(4m)
13C NMR (CDCl3, 75 MHz):  = 168.7, 154.0, 107.3, 42.0, 30.6, 26.0,
White solid; yield: 0.135 g (0.385 mmol, 77%); mp 175–177 °C.
25.9, 20.7.
IR (KBr): 3070, 3032, 2921, 1769, 1612, 1504, 1371, 1210, 1194, 1175,
1034, 1014, 882, 810, 664, 606, 564, 541, 469 cm–1
.
HRMS (ESI): m/z [M + Na]+ calcd for C20H30O4Na: 357.2036; found:
1H NMR (CDCl3, 300 MHz):  = 7.38 (d, J = 8.1 Hz, 4 H, ArH), 7.19 (d, J =
357.2035.
8.1 Hz, 4 H, ArH), 6.53 (s, 2 H, =CH), 2.38 (s, 12 H, CH3).
(Z,Z)-1,6-Diphenylhexa-2,4-diene-2,5-diyl Diacetate (4i)
White solid; yield: 0.135 g (0.385 mmol, 77%); mp 102–104 °C.
IR (KBr): 3070, 3026, 2952, 1748, 1635, 1494, 1455, 1436, 1364, 1202,
13C NMR (CDCl3, 75 MHz):  = 168.6, 147.9, 138.9, 131.8, 129.4, 124.6,
109.6, 21.3, 20.8.
HRMS (ESI): m/z [M + Na]+ calcd for C22H22O4Na: 373.1410; found:
373.1412.
1151, 1114, 1014, 943, 877, 794, 751, 705, 633, 594, 564, 472 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 7.33–7.21 (m, 10 H, ArH), 5.68 (s, 2 H,
=CH), 3.63 (s, 4 H, CH2), 2.06 (s, 6 H, CH3).
(Z,Z)-1,4-Bis(4-fluorophenyl)buta-1,3-diene-1,4-diyl Diacetate
(4n)
13C NMR (CDCl3, 75 MHz):  = 168.5, 149.2, 136.6, 129.2, 128.5, 126.8,
Pale yellow solid; yield: 0.122 g (0.340 mmol, 68%); mp 164–166 °C.
110.7, 39.9, 20.6.
HRMS (ESI): m/z [M + Na]+ calcd for C22H22O4Na: 373.1410; found:
373.1415.
IR (KBr): 3070, 2933, 1760, 1614, 1503, 1365, 1230, 1188, 1157, 1041,
913, 878, 836, 820, 753, 609, 566, 533 cm–1
.
1H NMR (DMSO-d6, 300 MHz):  = 7.67 (br, 4 H, ArH), 7.24 (br, 4 H,
(Z,Z)-1,8-Diphenylocta-3,5-diene-3,6-diyl Diacetate (4j)
ArH), 6.64 (s, 2 H, =CH), 2.43 (s, 6 H, CH3).
13C NMR (DMSO-d6, 101 MHz):  = 169.4, 162.8 (d, J = 247.0 Hz),
146.9, 130.9 (d, J = 2.8 Hz), 127.4 (d, J = 8.2 Hz), 116.1 (d, J = 21.8 Hz),
110.5, 21.1.
White solid; yield: 0.140 g (0.370 mmol, 74%); mp 97–99 °C.
IR (KBr): 3061, 3023, 2898, 1737, 1651, 1602, 1495, 1431, 1372, 1358,
1266, 1220, 1102, 1026, 947, 857, 790, 741, 697, 608, 583, 556, 491
cm–1
.
19F NMR (DMSO-d6, 282 MHz):  = –112.4.
1H NMR (CDCl3, 300 MHz):  = 7.38–7.19 (m, 10 H, ArH), 5.67 (s, 2 H,
=CH), 2.81 (t, J = 7.8 Hz, 4 H, CH2), 2.62 (t, J = 7.8 Hz, 4 H, CH2), 2.13 (s,
6 H, CH3).
HRMS (ESI): m/z [M + Na]+ calcd for C20H16O4F2Na: 381.0909; found:
381.0913.
13C NMR (CDCl3, 75 MHz):  = 168.6, 149.3, 140.9, 128.4, 128.3, 126.1,
(Z,Z)-1,4-Bis(3-methoxyphenyl)buta-1,3-diene-1,4-diyl Diacetate
109.6, 35.3, 33.1, 20.7.
(4o)
HRMS (ESI): m/z [M + Na]+ calcd for C24H26O4Na: 401.1723; found:
White solid; yield: 0.155 g (0.405 mmol, 81%); mp 189–191 °C.
401.1725.
IR (KBr): 3076, 2941, 2839, 1761, 1600, 1575, 1482, 1438, 1372, 1298,
1259, 1210, 1187, 1033, 917, 842, 781, 682, 580, 506 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

G
J. Francos, V. Cadierno
Paper
Synthesis
1H NMR (CDCl3, 300 MHz):  = 7.31 (t, J = 8.0 Hz, 2 H, ArH), 7.10 (d, J =
8.0 Hz, 2 H, ArH), 7.01 (d, J = 2.1 Hz, 2 H, ArH), 6.89 (dd, J = 8.0, 2.1 Hz,
2 H, ArH), 6.57 (s, 2 H, =CH), 3.85 (s, 6 H, OCH3), 2.38 (s, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 168.6, 159.8, 147.9, 136.1, 129.8, 117.3,
113.9, 110.9, 110.6, 55.3, 20.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(3-cyclopentylpropanoate) (4t)
White solid; yield: 0.121 g (0.271 mmol, 54%); mp 54–56 °C.
IR (KBr): 2951, 2868, 1740, 1649, 1467, 1420, 1381, 1355, 1303, 1262,
1153, 1130, 999, 930, 883, 829, 731, 563, 441 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.63 (s, 2 H, =CH), 2.47 (t, J = 7.8 Hz, 4
H, CH2), 2.26 (t, J = 6.9 Hz, 4 H, CH2), 1.82–1.15 (m, 30 H, CH2 + CH),
0.90 (t, J = 7.2 Hz, 6 H, CH3).
HRMS (ESI): m/z [M + Na]+ calcd for C22H22O6Na: 405.1309; found:
405.1311.
13C NMR (CDCl3, 75 MHz):  = 171.5, 149.8, 109.0, 39.6, 33.6, 33.3,
32.4, 31.3, 28.7, 25.1, 22.1, 13.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Dipropionate (4p)
White solid; yield: 0.123 g (0.396 mmol, 79%); mp 55–57 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C28H46O4Na: 469.3288; found:
IR (KBr): 2984, 2939, 2872, 1749, 1645, 1454, 1413, 1364, 1303, 1151,
469.3287.
1130, 931, 869, 822, 807, 731, 558 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.62 (s, 2 H, =CH), 2.47 (q, J = 7.5 Hz, 4
H, CH2), 2.25 (t, J = 7.2 Hz, 4 H, CH2), 1.46–1.28 (m, 8 H, CH2), 1.21 (t,
J = 7.5 Hz, 6 H, CH3), 0.89 (t, J = 7.2 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 172.0, 149.7, 108.9, 33.3, 28.7, 27.5,
22.1, 13.8, 9.2.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(2-phenylacetate) (4u)
White solid; yield: 0.167 g (0.384 mmol, 77%); mp 56–58 °C.
IR (KBr): 2951, 2848, 1733, 1652, 1454, 1327, 1298, 1231, 1118, 1052,
944, 876, 809, 717, 692, 550, 479 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 7.37–7.30 (m, 10 H, ArH), 5.30 (s, 2 H,
=CH), 3.72 (s, 4 H, CH2), 2.11 (t, J = 7.2 Hz, 4 H, CH2), 1.25–1.21 (m, 8 H,
CH2), 0.86 (t, J = 6.6 Hz, 6 H, CH3).
HRMS (ESI): m/z [M + H]+ calcd for C18H31O4: 311.2217; found:
311.2219.
13C NMR (CDCl3, 75 MHz):  = 169.1, 149.8, 133.7, 129.3, 128.7, 127.3,
108.9, 41.6, 33.1, 28.5, 22.1, 13.8.
HRMS (ESI): m/z [M + Na]+ calcd for C28H34O4Na: 457.2349; found:
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Diheptanoate (4q)
Colorless oil; yield: 0.173 g (0.409 mmol, 82%).
IR (film): 2956, 2930, 2860, 1752, 1643, 1467, 1433, 1379, 1210,
457.2347.
1127, 1049, 937, 829, 727 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.64 (s, 2 H, =CH), 2.46 (t, J = 7.5 Hz, 4
H, CH2), 2.27 (t, J = 6.9 Hz, 4 H, CH2), 1.77–1.67 (m, 4 H, CH2), 1.46–
1.34 (m, 20 H, CH2), 0.93–0.89 (m, 12 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 171.5, 149.8, 109.0, 34.3, 33.4, 31.4,
28.8, 28.7, 25.1, 22.5, 22.1, 14.0, 13.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(2-methylpropanoate) (4v)
Colorless oil; yield: 0.151 g (0.446 mmol, 89%).
IR (film): 2959, 2934, 2874, 1753, 1644, 1469, 1386, 1343, 1233,
1182, 1120, 1095, 1052, 935, 828, 748 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.64 (s, 2 H, =CH), 2.70 (sept, J = 6.9 Hz,
2 H, CH), 2.27 (t, J = 6.9 Hz, 4 H, CH2), 1.43–1.32 (m, 8 H, CH2), 1.28 (d,
J = 6.9 Hz, 12 H, CH3), 0.90 (t, J = 7.2 Hz, 6 H, CH3).
HRMS (ESI): m/z [M + Na]+ calcd for C26H46O4Na: 445.3288; found:
445.3287.
13C NMR (CDCl3, 75 MHz):  = 174.7, 149.7, 108.8, 34.1, 33.2, 28.6,
22.1, 19.0, 13.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Dioctanoate (4r)
White solid; yield: 0.185 g (0.410 mmol, 82%); mp 47–49 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C20H34O4Na: 361.2349; found:
IR (KBr): 2927, 2871, 1742, 1641, 1468, 1418, 1380, 1321, 1271, 1224,
361.2345.
1154, 1123, 938, 877, 842, 770, 720, 580, 481 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.64 (s, 2 H, =CH), 2.46 (t, J = 7.2 Hz, 4
H, CH2), 2.27 (t, J = 6.9 Hz, 4 H, CH2), 1.77–1.67 (m, 4 H, CH2), 1.46–
1.32 (m, 24 H, CH2), 0.91 (t, J = 6.9 Hz, 12 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 171.5, 149.8, 109.0, 34.3, 33.4, 31.7,
29.1, 28.9, 28.7, 25.1, 22.6, 22.1, 14.0, 13.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(2,2-dimethylpropanoate) (4w)
Colorless oil; yield: 0.079 g (0.215 mmol, 43%).
IR (film): 2959, 2933, 2873, 1747, 1645, 1480, 1462, 1396, 1369,
1263, 1114, 1029, 938, 843, 761 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.63 (s, 2 H, =CH), 2.25 (t, J = 6.9 Hz, 4
H, CH2), 1.45–1.31 (m, 8 H, CH2), 1.27 (s, 18 H, CH3), 0.90 (t, J = 6.9 Hz,
6 H, CH3).
HRMS (ESI): m/z [M + Na]+ calcd for C28H50O4Na: 473.3601; found:
473.3595.
13C NMR (CDCl3, 75 MHz):  = 176.1, 149.7, 108.8, 39.1, 33.1, 28.5,
27.2, 22.0, 13.8.
HRMS (ESI): m/z [M + Na]+ calcd for C22H38O4Na: 389.2662; found:
389.2655.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(3-bromopropanoate) (4s)
White solid; yield: 0.175 g (0.374 mmol, 75%); mp 66–68 °C.
IR (KBr): 2960, 2941, 2874, 1747, 1643, 1467, 1427, 1336, 1285, 1217,
1132, 1109, 952, 884, 816, 668, 580, 548 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 5.74 (s, 2 H, =CH), 3.65 (t, J = 6.4 Hz, 4
H, CH2Br), 3.08 (t, J = 6.4 Hz, 4 H, CH2CH2Br), 2.27 (t, J = 7.6 Hz, 4 H,
CH2), 1.46–1.40 (m, 4 H, CH2), 1.35–1.29 (m, 4 H, CH2), 0.89 (t, J = 7.2
Hz, 6 H, CH3).
13C NMR (CDCl3, 101 MHz):  = 168.1, 149.8, 109.3, 37.7, 33.3, 28.7,
25.8, 22.1, 13.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Dicyclopropanecarboxylate (4x)
White solid; yield: 0.140 g (0.418 mmol, 84%); mp 64–67 °C.
IR (KBr): 2940, 2870, 1734, 1646, 1456, 1445, 1382, 1307, 1266, 1143,
1124, 1098, 1029, 932, 848, 824, 737, 695, 633, 557, 473 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.65 (s, 2 H, =CH), 2.27 (t, J = 6.9 Hz, 4
H, CH2), 1.75–1.72 (m, 2 H, CH), 1.46–1.30 (m, 8 H, CH2), 1.13–1.10
(m, 4 H, CH2), 0.99–0.95 (m, 4 H, CH2), 0.91 (t, J = 7.2 Hz, 6 H, CH3).
HRMS (ESI): m/z [M + Na]+ calcd for C18H28Br2O4Na: 489.0247; found:
489.0247.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

H
J. Francos, V. Cadierno
Paper
Synthesis
13C NMR (CDCl3, 75 MHz):  = 172.5, 149.7, 109.0, 33.3, 28.7, 22.1,
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(4-vinylbenzoate) (4ac)
13.8, 12.8, 8.8.
White solid; yield: 0.147 g (0.320 mmol, 64%); mp 140–142 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C20H30O4Na: 357.2036; found:
357.2034.
IR (KBr): 2953, 2929, 2871, 1721, 1646, 1606, 1466, 1406, 1256, 1236,
1177, 1104, 1076, 1016, 932, 855, 780, 709, 599 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 8.12 (d, J = 8.4 Hz, 4 H, ArH), 7.55 (d, J =
8.4 Hz, 4 H, ArH), 6.81 (dd, J = 17.4, 11.1 Hz, 2 H, =CH), 5.93 (d, J = 17.4
Hz, 2 H, =CH2), 5.84 (s, 2 H, =CH), 5.45 (d, J = 11.1 Hz, 2 H, =CH2), 2.37
(t, J = 7.2 Hz, 4 H, CH2), 1.50–1.43 (m, 4 H, CH2), 1.40–1.26 (m, 4 H,
CH2), 0.86 (t, J = 7.2 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 163.9, 150.2, 142.5, 135.9, 130.4, 128.6,
126.3, 116.9, 109.5, 33.5, 28.8, 22.2, 13.8.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Dicyclohexanecarboxylate (4y)
White solid; yield: 0.176 g (0.420 mmol, 84%); mp 79–81 °C.
IR (KBr): 2929, 2858, 2669, 1749, 1643, 1451, 1376, 1311, 1241, 1211,
1152, 1117, 1018, 937, 896, 870, 831, 743, 694, 612, 547, 488 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 5.63 (s, 2 H, =CH), 2.50–2.43 (m, 2 H,
CH), 2.25 (t, J = 6.3 Hz, 4 H, CH2), 2.03–1.99 (m, 4 H, CH2), 1.79–1.32
(m, 24 H, CH2), 0.90 (t, J = 6.9 Hz, 6 H, CH3).
HRMS (ESI): m/z [M + H]+ calcd for C30H35O4: 459.2530; found:
13C NMR (CDCl3, 75 MHz):  = 173.7, 149.7, 108.9, 43.2, 33.3, 29.1,
459.2528.
28.6, 25.7, 25.4, 22.1, 13.9.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(3-methylbenzoate) (4ad)
White solid; yield: 0.126 g (0.290 mmol, 58%); mp 162–164 °C.
IR (KBr): 2956, 2928, 2871, 1726, 1611, 1466, 1422, 1286, 1262, 1184,
HRMS (ESI): m/z [M + Na]+ calcd for C26H42O4Na: 441.2975; found:
441.2976.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Dibenzoate (4z)
1107, 916, 882, 810, 778, 737, 679, 622 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 8.01–7.98 (m, 4 H, ArH), 7.49–7.40 (m,
4 H, ArH), 5.88 (s, 2 H, =CH), 2.48 (s, 6 H, CH3), 2.40 (t, J = 7.2 Hz, 4 H,
CH2), 1.51–1.46 (m, 4 H, CH2), 1.38–1.31 (m, 4 H, CH2), 0.88 (t, J = 7.2
Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 164.5, 150.2, 138.5, 134.3, 130.6, 129.5,
128.5, 127.2, 109.6, 33.5, 28.8, 22.2, 21.3, 13.8.
White solid; yield: 0.112 g (0.275 mmol, 55%); mp 159–161 °C.
IR (KBr): 2955, 2926, 2861, 1724, 1652, 1600, 1452, 1284, 1257, 1238,
1174, 1108, 1064, 1025, 865, 800, 702, 682, 622 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 8.18 (d, J = 7.5 Hz, 4 H, ArH), 7.68–7.51
(m, 6 H, ArH), 5.86 (s, 2 H, =CH), 2.38 (t, J = 7.3 Hz, 4 H, CH2), 1.49–1.44
(m, 4 H, CH2), 1.36–1.29 (m, 4 H, CH2), 0.86 (t, J = 7.0 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 164.3, 150.2, 133.5, 130.1, 129.5, 128.6,
109.6, 33.5, 28.8, 22.2, 13.8.
HRMS (ESI): m/z [M + Na]+ calcd for C28H34O4Na: 457.2349; found:
457.2348.
HRMS (ESI): m/z [M + Na]+ calcd for C26H30O4Na: 429.2036; found:
429.2039.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(thiophene-2-carboxylate)
(4ae)
White solid; yield: 0.090 g (0.215 mmol, 43%); mp 92–94 °C.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(4-methoxybenzoate) (4aa)
White solid; yield: 0.124 g (0.266 mmol, 53%); mp 170–172 °C.
IR (KBr): 2956, 2931, 2872, 1717, 1644, 1605, 1511, 1461, 1321, 1288,
IR (KBr): 2954, 2928, 2861, 1725, 1643, 1519, 1467, 1413, 1359, 1242,
1217, 1101, 1063, 861, 820, 777, 743, 711, 603, 541 cm–1
.
1H NMR (CDCl3, 400 MHz):  = 7.93 (dd, J = 4.0, 1.2 Hz, 2 H, Thienyl-
H), 7.66 (dd, J = 5.2, 1.2 Hz, 2 H, Thienyl-H), 7.18 (dd, J = 5.2, 4.0 Hz, 2
H, Thienyl-H), 5.85 (s, 2 H, =CH), 2.38 (t, J = 7.2 Hz, 4 H, CH2), 1.50–
1.45 (m, 4 H, CH2), 1.43–1.28 (m, 4 H, CH2), 0.87 (t, J = 7.2 Hz, 6 H,
CH3).
13C NMR (CDCl3, 101 MHz):  = 159.8, 149.9, 134.4, 133.3, 132.9,
128.0, 109.7, 33.4, 28.8, 22.2, 13.8.
1253, 1165, 1103, 1074, 1028, 844, 766, 694, 599 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 8.12 (d, J = 8.9 Hz, 4 H, ArH), 7.01 (d, J =
8.9 Hz, 4 H, ArH), 5.83 (s, 2 H, =CH), 3.92 (s, 6 H, OCH3), 2.36 (t, J = 7.2
Hz, 4 H, CH2), 1.50–1.40 (m, 4 H, CH2), 1.38–1.26 (m, 4 H, CH2), 0.86 (t,
J = 6.9 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 164.1, 163.8, 150.1, 132.2, 121.9, 113.8,
109.6, 55.5, 33.5, 28.8, 22.2, 13.8.
HRMS (ESI): m/z [M + Na]+ calcd for C22H26O4S2Na: 441.1165; found:
441.1160.
HRMS (ESI): m/z [M + Na]+ calcd for C28H34O6Na: 489.2253; found:
489.2248.
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(tetrahydrofuran-2-carboxyl-
ate) (4af)
(Z,Z)-Dodeca-5,7-diene-5,8-diyl Bis(4-fluorobenzoate) (4ab)
White solid; yield: 0.135 g (0.305 mmol, 61%); mp 165–167 °C.
IR (KBr): 3079, 2954, 2930, 2872, 1728, 1646, 1603, 1507, 1414, 1280,
Colorless oil; yield: 0.079 g (0.200 mmol, 40%).
IR (film): 2956, 2932, 2873, 1767, 1645, 1466, 1348, 1245, 1154,
1234, 1156, 1104, 1072, 1011, 858, 839, 764, 686, 597 cm–1
.
1129, 1084, 964, 930, 883, 839, 744 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 8.18 (dd, J = 8.4, 5.4 Hz, 4 H, ArH), 7.20
(t, J = 8.4 Hz, 4 H, ArH), 5.81 (s, 2 H, =CH), 2.36 (t, J = 7.2 Hz, 4 H, CH2),
1.47–1.40 (m, 4 H, CH2), 1.38–1.28 (m, 4 H, CH2), 0.86 (t, J = 7.2 Hz, 6
H, CH3).
13C NMR (CDCl3, 75 MHz):  = 166.1 (d, J = 254.9 Hz), 163.3, 150.1,
132.6 (d, J = 9.4 Hz), 125.6, 115.8 (d, J = 22.0 Hz), 109.5, 33.4, 28.8,
22.1, 13.8.
1H NMR (CDCl3, 300 MHz):  = 5.64 (s, 2 H, =CH), 4.60 (dd, J = 8.1, 5.1
Hz, 2 H, OCH), 4.07–3.95 (m, 4 H, OCH2), 2.41–2.29 (m, 2 H, OCHCH2),
2.27 (t, J = 7.2 Hz, 4 H, CH2), 2.12–2.09 (m, 2 H, OCH2CH2), 2.02–1.96
(m, 4 H, CH2), 1.42–1.30 (m, 8 H, CH2), 0.88 (t, J = 7.2 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 171.0, 149.6, 109.0, 76.5, 69.5, 33.1,
30.4, 28.6, 25.3, 22.1, 13.8.
HRMS (ESI): m/z [M + H]+ calcd for C22H35O6: 395.2428; found:
395.2430.
19F NMR (CDCl3, 282 MHz):  = –104.6.
HRMS (ESI): m/z [M + Na]+ calcd for C26H28F2O4Na: 465.1848; found:
465.1845.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J

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J. Francos, V. Cadierno
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Synthesis
(Z,Z)-Dodeca-5,7-diene-5,8-diyl (E,E)-Bis(3-phenylacrylate) (4ag)
White solid; yield: 0.101 g (0.220 mmol, 44%); mp 115–117 °C.
IR (KBr): 2960, 2931, 2859, 1722, 1634, 1579, 1467, 1423, 1326, 1308,
(2) See, for example: (a) Burk, M. J.; Kalberg, C. S.; Pizzano, A. J. Am.
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Paetzold, J.; Jensen, J. F. Org. Lett. 2003, 5, 3099. (d) Zhang, X.;
Huang, K.; Hou, G.; Cao, B.; Zhang, X. Angew. Chem. Int. Ed. 2010,
49, 6421. (e) Mamone, P.; Grünberg, M. F.; Fromm, A.; Khan, B.
A.; Gooßen, L. J. Org. Lett. 2012, 14, 3716. (f) Liu, Y.; Wang, Z.;
Ding, K. Tetrahedron 2012, 68, 7581. (g) Núñez-Rico, J. L.; Etayo,
P.; Fernández-Pérez, H.; Vidal-Ferran, A. Adv. Synth. Catal. 2012,
354, 3025. (h) Konrad, T. M.; Schmitz, P.; Leitner, W.; Franciò, G.
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19, 16209. (j) Arena, G.; Barreca, G.; Carcone, L.; Cini, E.; Marras,
G.; Nedden, H. G.; Rasparini, M.; Roseblade, S.; Russo, A.; Taddei,
M.; Zanotti-Gerosa, A. Adv. Synth. Catal. 2013, 355, 1449.
(k) Kleman, P.; González-Liste, P. J.; García-Garrido, S. E.;
Cadierno, V.; Pizzano, A. ACS Catal. 2014, 4, 4398. (l) Jia, J.; Fan,
D.; Zhang, J.; Zhang, Z.; Zhang, W. Adv. Synth. Catal. 2018, 360,
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W. Org. Lett. 2018, 20, 108.
1271, 1141, 1112, 979, 860, 766, 706, 680, 566, 481 cm–1
.
1H NMR (CDCl3, 300 MHz):  = 7.83 (d, J = 15.9 Hz, 2 H, =CH), 7.61 (br,
4 H, ArH), 7.45 (br, 6 H, ArH), 6.58 (d, J = 15.9 Hz, 2 H, =CH), 5.80 (s, 2
H, =CH), 2.36 (t, J = 6.9 Hz, 4 H, CH2), 1.53–1.29 (m, 8 H, CH2), 0.90 (t,
J = 7.2 Hz, 6 H, CH3).
13C NMR (CDCl3, 75 MHz):  = 164.6, 150.0, 146.3, 134.2, 130.7, 129.0,
128.3, 117.2, 109.4, 33.5, 28.8, 22.2, 13.9.
HRMS (ESI): m/z [M + Na]+ calcd for C30H34O4Na: 481.2349; found:
481.2347.
Funding Information
This work was supported by the Spanish MINECO Secretaría de Esta-
do de Investigación, Desarrollo e Innovación (CTQ2016-75986-P) and
the University of Oviedo (PAPI-18-GR-2011-0032).
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(3) Zhang, C.; Chen, L.; Chen, K.; Wang, C.; Xu, Z.; Jiang, H.; Zhu, S.
Org. Chem. Front. 2018, 5, 2510; and references cited therein.
(4) For reviews covering this topic, see: (a) Alonso, F.; Beletskaya, I.
P.; Yus, M. Chem. Rev. 2004, 104, 3079. (b) Beller, M.; Seayard, J.;
Tillack, A.; Jiao, H. Angew. Chem. Int. Ed. 2004, 43, 3368.
(c) Gooßen, L. J.; Rodríguez, N.; Gooßen, K. Angew. Chem. Int. Ed.
2008, 47, 3100. (d) Hintermann, L. Top. Organomet. Chem. 2010,
31, 123. (e) Bruneau, C. Top. Organomet. Chem. 2011, 43, 203.
(f) González-Liste, P. J.; Francos, J.; García-Garrido, S. E.;
Cadierno, V. ARKIVOC 2018, (ii), 17.
Acknowledgment
We thank Dr. Pedro J. González-Liste and Dr. Sergio E. García-Garrido
for helpful discussions and comments.
Supporting Information
Supporting information for this article is available online at
(5) For very recent examples, see: (a) Stark, M. J.; Tang, D. T.; Rath,
N. P.; Bauer, E. B. Tetrahedron Lett. 2018, 59, 873. (b) Chen, J.-F.;
Li, C. Org. Lett. 2018, 20, 6719. (c) Kukui, N.; Hinoue, T.;
Yoshinosuke, U.; Satoh, T. Chem. Lett. 2018, 47, 141.
https://doi.org/10.1055/s-0037-1610709.
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J