A Broad-Spectrum Synthesis of Tetravinylethylenes

Article abstract of DOI:10.1002/chem.201900550

The first general synthesis of compounds of the tetravinylethylene (TVE) family is reported. Ramirez-type dibromo-olefination of readily accessible penta-1,4-dien-3-ones generates 3,3-dibromo[3]dendralenes, which undergo twofold Negishi, Suzuki–Miyaura or Mizoroki–Heck reactions with a wide variety of olefinic coupling partners. This route delivers a broad range of unsymmetrically substituted tetravinylethylenes with up to three different alkenyl substituents attached to the central C=C bond. The extensive scope of the approach is demonstrated by the preparation of the first higher order oligo-alkenic through-conjugated/cross-conjugated hybrid compounds. An unsymmetrically substituted TVE is shown to undergo a domino electrocyclization–cycloaddition with high site-selectivity and diastereoselectivity, thereby demonstrating the substantial synthetic potential of substituted TVEs for controlled, rapid structural complexity generation.

Full text of DOI:10.1002/chem.201900550

A Journal of
Accepted Article
Title: A Broad-Spectrum Synthesis of Tetravinylethylenes
Authors: Michael Sherburn, Kelsey Horvath, Kimberley Roper,
Christopher Newton, and Jas S Ward
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201900550
Link to VoR: http://dx.doi.org/10.1002/chem.201900550
Supported by

10.1002/chem.201900550
Chemistry - A European Journal
COMMUNICATION
A Broad-Spectrum Synthesis of Tetravinylethylenes
Kelsey L. Horvath,[a] Christopher G. Newton,[a] Kimberley A. Roper,[a] Jas S. Ward[a] and
Michael S. Sherburn*[a]
syntheses reported in the literature,7 is only suited to the
attachment of four identical substituted alkenyl-groups to the
central C=C core.
Abstract: The first general synthesis of compounds of the
tetravinylethylene (TVE) family is reported. Ramirez-type dibromo-
olefination of readily accessible penta-1,4-dien-3-ones generates
3,3-dibromo[3]dendralenes, which undergo twofold Negishi, Suzuki-
Miyaura or Mizoroki-Heck reactions with a wide variety of olefinic
introduction to TVE
coupling partners. This route delivers
a
broad range of
π-system contains
through-conjugated
unsymmetrically–substituted tetravinylethylenes with up to three
different alkenyl substituents attached to the central C=C bond. The
extensive scope of the approach is demonstrated by the preparation
of the first higher order oligo-alkenic through-conjugated/cross-
conjugated hybrid compounds. An unsymmetrically-substituted TVE
is shown to undergo a domino electrocyclization-cycloaddition with
high site-selectivity and diastereoselectivity, thereby demonstrating
the substantial synthetic potential of substituted TVEs for controlled,
rapid structural complexity generation.
and
Z
E
cross-conjugated
triene segments
R
R
R
R
previous work4,5
Pd(OAc)2
XPhos, 60 °C
R
Cl
Cl
+
49–90%
Bu3Sn
Cl
Cl
5 examples
(>4 mol equiv)
Tetravinylethylene (TVE) is one of the smallest structures
exhibiting both through-conjugation and cross-conjugation
(Scheme 1). Specifically, the structure comprises intersecting
pairs of (E)-1,3,5-hexatrienes, (Z)-1,3,5-hexatrienes and 2-
methylene-1,4-pentadienes ([3]dendralenes). Nothing is known
about the impact of substitution upon the behavior of TVEs and
how this might be exploited. Furthermore, related structures
containing more than five C=C units have not been reported in
the literature. The first synthesis of TVE, a landmark contribution
from the classical era of unsaturated hydrocarbon chemistry,
was reported by Skattebøl and co-workers in the 1960s.1-3 We
recently disclosed the first preparatively useful approach to TVE,
a one-step multi-gram scale synthesis, and demonstrated that
the hydrocarbon is bench-stable when stored as a neat liquid.4,5
The one-step synthesis of TVE (Scheme 1, 1a) utilized a Pd(0)-
catalyzed fourfold Stille cross-coupling sequence between
tetrachloro-ethylene 2 and vinyltributylstannane 3a. In addition to
the parent TVE, five symmetrically-substituted TVEs 1b were
similarly prepared using substituted alkenyltributylstannanes 3b
in the exhaustive Stille cross-coupling process.4,5
2
R=H, Ph, CO2Me, 1a, R=H, TVE
CH2OTBS, TMS
1b, R≠H
3a, R=H
3b, R≠H
• fourfold Stille approach to TVE and symmetrically-substituted TVEs
R
R
this work
twofold
cross-
Br
Br
O
dibromo-
coupling
olefination
25 examples
R2
R1
14 examples
R1
R2
R1
R2
4
5
6
• first synthesis of unsymmetrically-substituted TVEs
• di-, tetra-, hexasubstituted TVEs with up to 3 different substituents
• no organotins: Negishi, Suzuki-Miyaura, Mizoroki-Heck reactions
Scheme 1. The existing synthetic route to TVEs with its limitations, and the
new, broad scope synthesis.
Herein we report a broad-reaching solution, delivering the first
29 unsymmetrically substituted TVEs carrying up to three
different substituents (Scheme 1, bottom). We also report the
first compounds exhibiting extended π-systems based upon TVE
subunits. Moreover, we establish the synthetic potential of these
unsymmetrically-substituted TVEs, by way of a one-pot, site-
selective and diastereoselective domino pericyclic sequence that
generates three C–C bonds and six contiguous stereocenters.
The new synthetic approach (Scheme 1, bottom) involves the
conversion of penta-1,4-dien-3-ones 4 (readily accessed through
As a starting point for future synthetic applications, the parent
TVE has been shown to rapidly generate multi-cyclic systems.4,5
Additionally, the hybrid through/cross-conjugated structure of the
TVE unit represents the smallest organic four-directional branch
point in a possible conducting molecular wire.6 To realize the
potential of the TVE family in target synthesis and materials
applications, synthetic access to unsymmetrically-substituted
systems must be granted. Until now, no unsymmetrically-
substituted TVEs have been reported. Our previous synthetic
approach (Scheme 1), in common with all other substituted TVE
twofold
aldol-type
condensations)
into
3,3-dibromo-
[3]dendralenes 5, which in turn undergo a range of twofold
cross-couplings to furnish diversely-substituted tetravinyl-
ethylenes 6.
Twelve substituted penta-1,4-dien-3-ones 4 were prepared, by
way of sequential Claisen-Schmidt condensations8 (see SI for
details). There are only three examples of Ramirez dibromo-
olefinations of penta-1,4-dien-3-ones 4 in the literature9-11 and, in
our hands, low yields were obtained under standard Ramirez
reaction conditions.12 Gratifyingly, in the majority of cases, the
modified protocol introduced by Lautens and co-workers13
[a]
Kelsey L. Horvath, Dr Christopher G.Newton,
Dr Kimberley A. Roper, Dr Jas S. Ward, Prof Michael S. Sherburn*
Research School of Chemistry
Australian National University
Canberra, ACT 2601 (Australia)
E-mail: michael.sherburn@anu.edu.au
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/chem.201900550
Chemistry - A European Journal
COMMUNICATION
furnished workable yields, and twelve substituted 3,3-
Br
Br
Br
dibromo[3]dendralenes14 5 were prepared in this manner (Table
same
alkenyl
substituent
7 examples
1).
R1
R1
R1
R1
5a-g
6a-g
6h-l
MgBr (3.5 mol equiv)
ZnBr2 (4.5 mol equiv)
[Pd(dppf)Cl2] (10 mol %)
THF, 30–35 °C
Br
Br
Br
Br
O
same
alkenyl
different
alkenyl
substituents
7 examples
substituent
R1
R1
R1
R1
5 examples
CBr4 (3 mol equiv)
(i-PrO)3P (6 mol equiv)
CH2Cl2
5a-g
R1
R2
R1
R2
4a-g
5h-l
Br
O
different
alkenyl
substituents
5 examples
R1
R2
R1
R2
4h-l
5h-l
Br
Br
Br
Br
X
X
6d, 78%
X = OMe; 6a, 75%
X = H; 6b, 91%
X = F; 6c, 73%
X
X
5d, 68%
Br Br
X = OMe; 5a, 62%
X = H; 5b, 64%
X = F; 5c, 47%
X
X
X = S; 6f, 75%
X = O; 6g, 79%
Br
Br
6e, 59%
X
X
X = S; 5f, 44%
X = O; 5g, 55%
5e, 71%
Br
Br
Br
Br
X
Y
X
X = OMe, Y = H; 6j, 80%
X = F, Y = H; 6k, 56%
X = F, Y = OMe; 6l, 43%
X = S; 6h, 60%
X = O; 6i, 64%
X
Y
X
X = OMe, Y = H; 5j, 46%
X = F, Y = H; 5k, 35%
X = F, Y = OMe; 5l, 29%
Table 2. Twofold Negishi cross-coupling of 3,3-dibromo[3]dendralenes 5 with
vinylzinc bromide furnishes the first unsymmetrical tetravinylethylenes 6.
X = S; 5h, 70%
X = O; 5i, 40%
Table 1. Lautens-modified Ramirez dibromo-olefination of penta-1,4-dien-3-
ones 4 permits the first general synthesis of 3,3-dibromo[3]dendralenes 5.
3,3-Dibromo[3]dendralenes comprising the same (5a-g) or
different (5h-l) alkenyl substituents performed equally well, to
generate the first examples of TVEs possessing two or three
different alkenyl groups about the central C=C bond. TVEs
bearing carbocyclic aromatic substituents with different
electronic characteristics (6j-l) and the first TVEs carrying
heterocyclic aromatic substituents (6f-i) are included in this
selection.
Unlike some other dendralenic structures, which exhibit a
propensity
to
dimerize
and
polymerize,15
3,3-
dibromo[3]dendralenes
5
are generally white or yellow
crystalline solids that can be stored neat without appreciable
decomposition, and are easily handled using standard laboratory
techniques.
Twofold cross-couplings of 3,3-dibromo[3]dendralenes 5 are
by no means limited to the introduction of a pair of unsubstituted
vinyl groups: in fact, alkenyl groups bearing substituents at any
position are tolerated. The syntheses of eighteen of these more
highly substituted TVEs are summarized in Table 3. Double
Negishi couplings of 3,3-dibromo[3]dendralene 5a with 2-
While there are many examples of cross-coupling reactions of
1,1-dibromoalkenes in the literature,16 there is only one example
of a cross-coupling of a 3,3-dibromo[3]dendralene, involving the
Sonogashira sp2–sp coupling of
a
cyclic system with
trimethylsilylacetylene.10 In light of the lack of precedent, both
for sp2–sp2 cross-couplings and also for reactions of acyclic
systems, we were delighted to find that twofold Negishi reactions
of 3,3-dibromo[3]dendralenes 5 with vinylzinc bromide proceed
well using [Pd(dppf)Cl2] as pre-catalyst to form the first
unsymmetrical TVEs 6 (Table 2).
propenyl-,
(E)-styrenyl-
and
(2-methylprop-1-en-1-yl)zinc
bromides furnished six novel tetra- and hexa-substituted TVEs
6n-s. Cross-couplings other than Negishi reactions are also
successful, as demonstrated by the products of double Suzuki-
Miyaura17 and Mizoroki-Heck18 processes, 6t-v (3 examples)
This article is protected by copyright. All rights reserved.

10.1002/chem.201900550
Chemistry - A European Journal
COMMUNICATION
and 6w-ae (9 examples), respectively. These results establish
the wide scope of the 3,3-dibromo[3]dendralene cross-coupling
approach to TVE synthesis and its broad tolerance of
substitution upon the incoming alkenyl-groups.
Following the trend previously seen,4,5 the 25 new TVEs
depicted in Tables 2 and 3 are bench-stable substances. No
special equipment or methods are required when manipulating
these compounds: they survive storage neat at ambient
temperature for several weeks. The lack of susceptibility of this
new family of π-bond rich systems towards uncatalyzed Diels-
Alder dimerization and autoxidation (typical of related cross-
conjugated15 and through-conjugated19 polyenic systems) bodes
well for future applications.
Br
Br
Br
same
alkenyl
14 examples
substituent
R1
R1
Access to unsymmetrically-substituted TVEs promotes new
opportunities in rapid structure complexity generation, and an
interesting question of diene site selection in [4+2]cycloadditions
of polyenes (Scheme 2). Heating diphenyl-di-(1-naphthyl)-TVE
6aa in benzene brings about a disrotatory electrocyclization to
generate cyclic [4]dendralene14 7, with a cis-disposition between
the two cyclohexadiene substituents. When performed in the
presence of dienophile N-tert-butylmaleimide 8, a subsequent
endo-mode cycloaddition occurs, with approach to the less
sterically encumbered π-diastereoface of [4]dendralene 7. The
13 unique alkenyl-
substituents introduced
R1
R1
5a,b,e
6m,p,r-ac
Br
3 distinct
coupling reactions
different
alkenyl
substituents
3 examples
R1 5i,l R2
R1
R2
6n,o,q
twofold Negishi couplings
Ph
Me
Me
ZnBr2 (4.5 mol equiv)
[Pd(dppf)Cl2] (10 mol %)
THF, 30–35 °C
BrMg
Me BrMg
BrMg
two non-equivalent semi-cyclic dienes of [4]dendralene
7
alkenyl Grignard reagent (3.5 mol equiv)
(highlighted in different colors in Scheme 2) are expected to be
more reactive than the cyclohexadiene site,5 and the phenyl-
substituted diene is preferred over the 1-naphthyl-substituted
site. Overall, this operationally trivial domino sequence
generates densely-functionalized decalin 9, with three new C–C
bonds, six contiguous stereocenters, and a cyclic [3]dendralene
subunit that invites additional synthetic manipulation.20
Me
Me
Me
Ph
Ph
Me
Me
Ph
Me
Ph
R1
R2
R1
R2
R1 = R2 = Ph, 6p, 71%
6m, 79%
R1 = Ph, R2 = 2-furyl, 6n,a 93%
R1 = 4-(MeO)C6H4-,
R1 = 4-(MeO)C6H4-, R2 = 4-(F)C6H4-, 6o, 56%
R2 = 4-(F)C6H4-, 6q, 71%
twofold Suzuki-Miyaura couplings
n-hex
[Pd2(dba)3] (2 mol %),
t-Bu3P•HBF4 (2.4 mol %)
KF•2H2O, THF, 20–22 °C
dienophile 8
(1 mol equiv)
(HO)2B
(HO)2B
Ph (HO)2B
C6D6, 110 °C
microwave
30 min
alkenyl boronic acid (3.0 mol equiv)
7
H
n-hex
n-hex
6π electro-
cyclization
H
O
Ph
Ph
Ph
Ph
O
8
N
t-Bu
6aa
Ph
Ph
Ph
Ph
53%;
site sel. = 84:16
[4+2] cyclo-
addition
6r, 59%
6s, 84%
6t, 83%
twofold Mizoroki-Heck couplings
X
O
[Pd2(dba)3] (5 mol %),
t-Bu3P•HBF4 (10 mol %)
Cy2NMe, dioxane, 20–22 °C
OR3
H
H
acrylate or styrene (5.0 mol equiv)
X
X
H
H
H
R3O2C
CO2R3
H
O
O
N
X-ray
t-Bu
R1 = Ph, X = Me, 6w, 88%
R1 = Ph, X = OMe, 6x,a 98%
R1 = Ph, X = F, 6y, 93%
9
Scheme 2. Stereoselective domino [6π]electrocyclization/[4+2]cycloaddition of
TVE 6ad proceeds with diene site selectivity to generate multicyclic product 9.
H atoms not attached to stereocenters are omitted from the X-ray crystal
structure22,23 for clarity.
R1
R1
R1 = Ph, X = Cl, 6z, 79%
Ph
Ph
R1 = 1-naphthyl, X = H, 6aa,a 70%
R3 = Et, 6u, 90%
R1 = 4-(MeO)C6H4-, X = NO2, 6ab, 54%
R3 = t-Bu, 6v, 88%
R1 = 4-(MeO)C6H4-, X = OMe, 6ac,a 70%
Table 3. Twofold Negishi, Suzuki-Miyaura or Mizoroki-Heck reactions grant
access to unsymmetrical, multi-substituted tetravinylethylenes. aX-ray crystal
structures of these four TVEs22 are in the SI.
This article is protected by copyright. All rights reserved.

10.1002/chem.201900550
Chemistry - A European Journal
COMMUNICATION
EtO2C
CO2Et
Br
Br
Br
Br
Br
Br
CO2Et
[Pd2(dba)3]
t-Bu3P•HBF4
Cy2NMe, 1,4-dioxane
53%
Br
Br
12
10
11
Ph
ZnBr2
[Pd(dppf)Cl2]
THF, 59%
BrMg
ZnBr2
[Pd(dppf)Cl2]
THF, 63%
EtO2C
CO2Et
BrMg
BrMg
17
BrMg
67%
62%
ZnBr2
[Pd(dppf)Cl2]
THF
14
15
16
13
X-ray
Scheme 3. First preparation of higher order acyclic C=C-based π-frameworks related to TVE. The new π-systems are highlighted in green. Ethyl groups are
truncated in the X-ray crystal structure22,23 for clarity.
The robust nature of the new pentaene-based TVE compounds,
combined with their ease of synthesis, prompted the question of
whether larger structures with unprecedented acyclic π-
frameworks were within reach. The successful extension of
Acknowledgements
these methods to the syntheses of hexaenes 14 and 15, and
heptaenes 13, 16 and 17 are depicted in Scheme 3. Dibromo-
tetraene 10, dibromo-pentaene 11 and tetrabromo-triene 12,
prepared through Lautens-modified Ramirez dibromo-olefination
reactions of commercially available ketonic precursors (see SI),
underwent twofold or fourfold Negishi or Mizoroki-Heck
couplings to furnish the bench-stable polyenic products. The UV
absorption spectrum of heptaene 17 exhibits features
attributable to the longest through-conjugated subunit (see SI).
The solid state molecular structure of tetra-ester 17, obtained
from single crystal X-ray analysis, is consistent with this
observation, revealing an essentially in-plane 2,4,6,8,10-
dodecapentaenoate unit (Scheme 3). Acyclic, hybrid cross-
conjugated/through-conjugated C=C structures are very poorly
represented in the literature.21 The structures depicted in
Scheme 3 represent the first examples of substances of this
type.
This work was supported by the Australian Research Council.
Keywords: hydrocarbons • polyenes • cross-coupling •
electrocyclic reactions • cycloaddition
[1]
[2]
[3]
L. Skattebøl, Acta. Chem. Scand. 1963, 17, 1683–1693.
L. Skattebøl, S. Solomon, J. Am. Chem. Soc. 1965, 87, 4506–4513.
L. Skattebøl, J. L. Charleton, P. deMayo, Tetrahedron Lett. 1966, 7,
2257–2260.
[4]
[5]
[6]
E. J. Lindeboom, A. C. Willis, M. N. Paddon-Row, M. S. Sherburn,
Angew. Chem. Int. Ed. 2014, 79, 5440–5443.
E. J. Lindeboom, A. C. Willis, M. N. Paddon-Row, M. S. Sherburn, J.
Org. Chem. 2014, 53, 11496–11507.
To our knowledge, only aromatic ring-based (and not C=C bond-based)
branch points have been reported. Despite their significant potential, it
was recently noted that branched molecular wires are rarely fabricated
in a precise manner: R. Sakamoto, S. Katagiri, H. Maeda, Y. Nishimori,
S. Miyashita, H. Nishihara, J. Am. Chem. Soc. 2015, 137, 734-741.
(a) R. W. Bost, J. A. Krynitsky, J. Am. Chem. Soc. 1948, 70, 1027–
1029; (b) F. Bohlmann, K. Kieslich, Abh. Braunschweig. Wiss. Gess.
1957, 147; (c) P. Cadiot, W. Chodkiewicz, J. Pauss-Godineau, Bull.
Soc. Chim. Fr. 1961, 2176–2193; (d) R. Kuhn, B. Schulz, Chem. Ber.
1963, 96, 3200–3208; (e) R. Kuhn, B. Schulz, Angew. Chem. 1963, 75,
452–453; (f) L. Lombardo, F. Sondheimer, Synthesis 1980, 950–952; (g)
J-M. Pons, M. Santelli, J. Org. Chem. 1989, 54, 877–884.
(a) L. Claisen, A. Claparède, Ber. 1881, 14, 349–353; (b) J. G. Schmidt,
Ber. 1881, 14, 1459–1461.
[7]
In summary, we have described the first general synthetic
approach to TVEs and related through/cross-conjugated acyclic
C=C-based systems. This work reports 34 new TVEs and
related structures, including the first examples exhibiting
unsymmetrical substitution patterns, extended through-
conjugation and/or cross-conjugation. The synthetic approach is
robust, involving twofold Negishi, Suzuki-Miyaura or Mizoroki-
Heck couplings of acyclic 3,3-dibromo[3]dendralenes. The new
structures are bench stable compounds that undergo
operationally simple, selective, complexity-generating domino
sequences. The acyclic C=C-bond-rich structures described
herein are representatives of a sizeable region of structural
space that was previously inaccessible but is now available for
exploration and investigation. Applications in target synthesis
and in conducting materials will follow.
[8]
[9]
(a) R. Kuhn, H. Fischer, D. Rewicki, H. Fischer, Liebigs Ann. Chem.
1965, 689, 1–20; (b) C. Raulet, E. Levas, Bull. Soc. Chim. Fr. 1971,
2598–2606.
[10] H. Hopf, J. Kampen, P. Bubenitschek, P. G. Jones, Eur. J. Org. Chem.
2002, 1708–1721.
[11] Dichloro-olefination
of
acyclic
penta-1,4-dien-3-ones
with
dichloroketene proceeds in low yields: J. Ojima, K. Itagawa, S. Hamai,
This article is protected by copyright. All rights reserved.

10.1002/chem.201900550
Chemistry - A European Journal
COMMUNICATION
T. Nakada, S. Kuroda, J. Chem. Soc., Perkin Trans. 1 1983, 2997–
3004.
[20] For important synthetic contributions involving cyclic [3]dendralenes
and their oxa-[3]dendralene analogs, see the following representative
papers (a) K. M. Brummond, H. Chen, P. Sill, L. You, J. Am. Chem. Soc.
2002, 124, 15186–15187; (b) S. Werner, D. M. Turner, P. G. Chambers,
K. M. Brummond, Tetrahedron 2008, 64, 6997–7007; (c) C. Spino, G.
Liu, J. Org. Chem. 1993, 58, 817–819; (d) S. Perreault, C. Spino, Org.
Lett. 2006, 8, 4385–4388.
[12] N. B. Desai, N. McKelvie, F. Ramirez, J. Am. Chem. Soc. 1962, 84,
1745–1747.
[13] (a) Y-Q. Fang, O. Lifchits, M. Lautens, Synlett 2008, 3, 413–417; (b) C.
Bryan, V. Aurregi, M. Lautens, Org. Synth. 2009, 86, 36–46.
[14] For a review on dendralenes, see: H. Hopf, M. S. Sherburn, Angew.
Chem., Int. Ed. 2012, 51, 2298-2338.
[21] Cross Conjugation: Modern Dendralene, Radialene and Fulvene
Chemistry, H. Hopf, M. S. Sherburn, eds., Wiley-VCH 2016. 464 pages.
ISBN 978-3-527-33437-7.
[15] (a) A. T. Blomquist, J. A. Verdol, J. Am. Chem. Soc. 1955, 77, 81–83;
(b) J. Mulzer, G. Brüntrup, U. Kühl and G. Hartz, Chem. Ber. 1982, 115,
3453–3469; (c) H. Toombs-Ruane, E. L. Pearson, M. N. Paddon-Row,
M. S. Sherburn, Chem. Commun. 2012, 48, 6639–6641.
[16] Reviews: (a) F. Legrand, K. Jouvin, G. Evano, Isr. J. Chem. 2010, 50,
588-604; (b) G. Chelucci, Chem. Rev. 2012, 112, 1344-1462.
[17] These transformations adapt conditions reported in S. Lou, G. C. Fu,
Adv. Synth. Catal. 2010, 352, 2081–2084.
[22] CCDC 1890206, 1890207, 1890208, 1890213, 1890214 and 1890215
contain the supplementary crystallographic data for this paper. These
data are provided free of charge by The Cambridge Crystallographic
Data Centre.
[23] Molecular structures from single crystal X-ray analyses were visualized
using CYLview 1.0b; C. Y. Legault, Université de Sherbrooke, 2009
(http://www.cylview.org)
[18] These reactions adapt the protocol described in A. F. Littke, G. C. Fu, J.
Am. Chem. Soc. 2001, 123, 6989–7000.
[19] F. Sondheimer, D. A. Ben-Efraim, R. Wolovsky, J. Am. Chem. Soc.
1961, 83, 1675–1681.
This article is protected by copyright. All rights reserved.

10.1002/chem.201900550
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Master key for TVE. The first
general synthesis of
Kelsey L. Horvath, Christopher G.
Newton, Kimberley A. Roper, Jas S.
Ward, Michael S. Sherburn*
tetravinylethylenes (TVEs) involves
the preparation and cross-coupling
of dibromo-[3]dendralenes. Their
value in controlled, rapid structural
complexity generation is
demonstrated. The first higher order
acyclic oligo-alkenic through-
conjugated/cross-conjugated hybrid
compounds are also reported.
3 step
sequence
Page No. – Page No.
A Broad-Spectrum Synthesis of
Tetravinylethylenes
substituted
tetravinylethylenes
This article is protected by copyright. All rights reserved.