Functionalization of (-)-β-pinene and (-)-limonene via cross metathesis with symmetrical internal olefins

Article abstract of DOI:10.1016/j.catcom.2019.105893

The straightforward functionalization of sterically demanding α,α-disubstituted double bonds of the natural products β-pinene and limonene via cross metathesis with symmetrical internal olefins is described. The reaction is catalyzed by Hoveyda-Grubbs type ruthenium catalysts in dimethyl carbonate as green solvent and makes possible the clean introduction of ester and nitrile groups in one step without formation of byproducts.

Full text of DOI:10.1016/j.catcom.2019.105893

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Functionalization of (-)-β-pinene and (-)-limonene via cross
metathesis with symmetrical internal olefins
Luciana Sarmento Fernandes, Dalmo Mandelli, Wagner A.
Carvalho, Cédric Fischmeister, Christian Bruneau
PII:
S1566-7367(19)30354-1
DOI:
https://doi.org/10.1016/j.catcom.2019.105893
CATCOM 105893
Reference:
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
10 October 2019
15 November 2019
25 November 2019
Please cite this article as: L.S. Fernandes, D. Mandelli, W.A. Carvalho, et al.,
Functionalization of (-)-β-pinene and (-)-limonene via cross metathesis with symmetrical
internal olefins, Catalysis Communications (2019), https://doi.org/10.1016/
j.catcom.2019.105893
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Functionalization of (-)--pinene and (-)-limonene via cross metathesis with symmetrical
internal olefins
Luciana Sarmento Fernandes,a,b Dalmo Mandelli,b Wagner A. Carvalho,b Cédric
Fischmeister,a Christian Bruneaua*
a Univ Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) - UMR6226,
35000 Rennes, France.
bCentro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André, Brazil
*Corresponding author: e-mail address: christian.bruneau@univ-rennes1.fr
Abstract
The straightforward functionalization of sterically demanding -disubstituted double bonds of the
natural products -pinene and limonene via cross metathesis with symmetrical internal olefins is
described. The reaction is catalyzed by Hoveyda-Grubbs type ruthenium catalysts in dimethyl
carbonate as green solvent and makes possible the clean introduction of ester and nitrile groups in one
step without formation of byproducts.
Keywords: cross metathesis, terpenes, ruthenium catalysis
1. Introduction
Cyclic terpenes such as α-pinene, β-pinene, camphene and limonene are important bio-
sourced components present in the resin of pine and citrus trees and are currently produced on
an industrial scale. The world production of turpentine, which contains mainly these terpenes,
is estimated at 350.000 tons/year [1], while that of limonene extracted from the peel of citrus
fruits produced in fruit juice industry, containing about 90% of limonene [2], could result in
approximately 65 kilotons per year [3]. Monoterpenes have already found direct applications
in the field of fragrances and flavors [4] and constitute renewable building blocks for the
access to sustainable polymers [5]. Several catalytic transformations of natural terpenes, such
as oxidation, epoxidation, hydroformylation, hydrogenation, dehydrogenation, isomerization,
rearrangement, have been achieved in order to produce added value chemicals for various
applications [6,7].
Olefin metathesis, in particular cross metathesis, has an enormous potential for direct
functionalization of olefins arising from natural resources [8,9]. The possibility of introducing

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ester, aldehyde, halogen, nitrile functional groups has already been demonstrated starting
from 1,2-disubstituted internal double bonds of fatty acid derivatives [10,11] and terpenes
featuring the trisubstituted prenyl end [12,13] with electron deficient olefins, allylic chlorides
and esters as cross metathesis partners. We were especially interested in the functionalization
of (1S)-(-)--pinene 1 and (S)-(-)-limonene 2 (Figure 1), which are bulky unsaturated
monoterpenes featuring a terminal disubstituted carbon-carbon double bond. The first
substrate is a sterically hindered methylenecyclohexane, and the second corresponds to a
propen-2-ylcyclohexene derivative.
Figure 1: Cyclic monoterpenes and ruthenium catalysts used in this study
A few examples of cross metathesis of gem-disubstituted cyclic olefins with terminal olefins have
been reported from methylene-cyclobutane, [14] -cyclopentane and -cyclohexane, [15] and the more
difficult cross metathesis of olefins with sterically encumbered exocyclic methylene groups is much
less documented [16,17]. Terpenes 1 and 2 have already been involved in olefin metathesis
reactions with ruthenium catalysts, especially as chain transfer agents during cleavage of
natural polyisoprene rubbers into terpene-terminated oligomers,[18] and during ring opening
metathesis polymerization of dicyclopentadiene to control crosslinking and physical
properties of the resulting polymers [19].
There are only few examples where these terpenes have been used as cross metathesis
partners with olefins to form new fine chemicals. Thus, limonene has been reacted with the
terminal olefin 1-hexene in the presence of 2 mol% of a second generation Grubbs catalyst
without solvent to give the expected butyl-substituted limonene as a E+Z mixture in 40%
yield [20]. The extension to the non-conjugated 1,5-hexadiene has led to polyhexadiene

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together with hexadiene oligomers featuring one or two limonene end. Under these conditions
-pinene is not reactive, and cross metathesis products have been obtained only with neutral
internal olefins partners using a ruthenium catalyst and a large excess of terpene [17,21]. On
the other hand, even though the exocyclic double bond of limonene was reactive in
intramolecular ring closing metathesis with an acrylic double bond, [22] a terminal electron
deficient olefin such as an acrylate did not react intermolecularly with these terpenes but only
provided the self-metathesis maleate/fumarate mixture [13]. These results showed that beside
the nature of the catalyst, which is also a crucial parameter, cross metathesis of the bulky
terpenes 1 and 2 with ruthenium catalysts took place favorably when the cross metathesis
partner presented an internal carbon-carbon double bond. This observation provided impetus
to investigate the ruthenium-catalyzed cross metathesis of terpenes 1 and 2 with symmetrical
functional olefins, namely acrylic and allylic derivatives, in order to generate only one cross
metathesis product.
2. Results and discussion
2.1. Cross metathesis of acrylic olefins with -pinene 1
We first investigated the cross metathesis reaction of -pinene 1 with dimethyl maleate 3 and
fumarate 4 as symmetrical functional olefin (Figure 2 (1)) in the presence of the commercially
available second generation ruthenium catalysts Ru1-Ru4 (Figure 1).

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Figure 2. Cross metathesis of -pinene 1 with various acrylic substrates
Most of the experiments were carried out in a closed Schlenk reactor under argon atmosphere
at 100 °C during 15 h and the results were based on GC analysis of crude mixtures. The effect
of temperature, concentration of substrates, catalyst loading and nature of the solvent were
first examined (Table 1).
Our first attempts revealed that good conversion of -pinene 1 into 5 was obtained with the
symmetrical electron deficient olefins 3 and 4 in the presence of 2.5 mol% of the Zhan-1-B
Ru1 and the Hoveyda Ru2 catalysts. Surprisingly, when the less hindered catalyst Ru3 and
the more bulky Z-selective catalyst Ru4 were used under the conditions of Table 1, entry 2
and 3, no conversion of -pinene was observed. We found that dimethyl carbonate as green
solvent provided better results than toluene, which is commonly used in olefin metathesis

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operating at high temperature. Indeed, a temperature of 100 °C was necessary to get high
conversion of the terpene and this temperature was adopted for further investigation. With
both olefins 3 and 4, the effect of the concentration of the terpene was relatively weak as its
conversion remained in the same range when the concentration was varied from 0.074 to 0.74
mol/L with the two catalysts (entries 4, 5; 9, 10; 14, 15; 17, 18). In addition, it was possible to
perform the cross metathesis reaction under neat conditions with an excess of fumarate 3 or
maleate 4 (entries 11, 19). On the other hand, a higher catalyst loading of 5 mol% appeared to
give slightly higher conversion than with 2.5 mol% (entries 4, 6; 8, 9; 16, 17).
Table 1 Cross metathesis of -pinene 1 with dimethyl maleate 3 and fumarate 4a
Entry 3/1 or 4/1
Catalyst
Conc.
Temp. Solvent
Conv. Yield
(E)/(Z)-5
(mol. ratio) (mol%)
(mol/L) (°C)
(%)b
51
61
55
67
69
77
76
70
85
91
80
54
43
59
55
69
85
74
57
(%)b (%)c ratiod
1
3/1 (2)
3/1 (2)
3/1 (2)
3/1 (4)
3/1 (4)
3/1 (4)
3/1 (4)
3/1 (4)
3/1 (4)
3/1 (4)
3/1
Ru1 (2.5)
0.37
0.37
0.37
0.37
0.074
0.37
0.74
0.37
0.37
0.74
115
130
100
100
100
100
100
100
100
100
100
115
100
100
100
100
100
100
100
toluene
toluene
DMC
DMC
DMC
DMC
DMC
DMC
DMC
DMC
neat
49
62:38
60:40
60:40
61:39
61:39
62:38
62:38
62:38
61:39
57:43
55:45
76:24
73:27
77:23
73:27
69:31
68:32
70:30
69:31
2
Ru1 (2.5)
Ru1 (2.5)
Ru1 (2.5)
Ru1 (2.5)
Ru1 (5)
57
3
47
4
66
5
48
6
70 (66)
72 (48)
68
7
Ru1 (5)
8
Ru2 (2.5)
Ru2 (5)
9
79 (57)
91 (65)
80
10
11
12
13
14
15
16
17
18
Ru2 (5)
Ru2 (5)
4/1 (2)
4/1 (2)
4/1 (2)
4/1 (4)
4/1 (4)
4/1 (4)
4/1 (4)
4/1
Ru1 (2.5)
Ru1 (2.5)
Ru1 (2.5)
Ru1 (2.5)
Ru2 (2.5)
Ru2 (5)
0.37
0.37
0.37
0.74
0.37
0.37
0.74
toluene
DMC
DMC
DMC
DMC
DMC
DMC
neat
52
37 (30)
58 (39)
47
66 (40)
79 (57)
71 (57)
52 (37)
Ru2 (5)
19
Ru2 (5)
a
b
General conditions: -pinene 1 (100 mg, 0.7 mmol), solvent (1, 2 or 10 mL), reaction time (15 h), Conversion
c
and GC yield determined using hexadecane as internal standard, Isolated yield, d E/Z ratio determined by GC of
the crude mixture.

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It is noteworthy that in a general manner, starting from fumarate or maleate, catalyst Ru2
provided the best conversion of -pinene 1. In all cases, due to the presence of an excess of
fumarate or maleate, a mixture of these two stereoisomers was observed at the end of the
reaction resulting from their self-metathesis reaction. In addition, we confirmed that when
methyl acrylate was used, no cross-metathesis product was formed, -pinene 1 was recovered
and only the self-metathesis products dimethyl fumarate 3 and maleate 4 were formed [13].
This result contrasts with the easy formation of cross metathesis products from acrylic acid
esters as well as maleate by cross metathesis with non-sterically hindered monosubstituted
terminal olefins [23,24]. Indeed, maleates and fumarates have been efficiently used in olefin
cross metathesis in place of acrylates, especially with the objective of reducing the number of
possible cross metathesis products, but they had never been shown to be suitable substrates
when acrylates did not work.
The cross metathesis of 1 with methyl acrylate can formally generate two types of ruthenium
carbene species: a methoxycarbonylmethylidene [Ru3] and a cyclohexylidene [Ru4]
(Figure 3). [Ru3] is a well-known ruthenium enoic carbene intermediate that has been
reported in catalytic transformations including self-metathesis of acrylates with second
generation ruthenium catalysts, and described as fast initiating but unstable olefin metathesis
catalyst [25]. The ruthenium moiety [Ru4] has been proposed as active species during the
previously reported metathesis transformations of -pinene with internal olefins,[17] and
proposed in predictive calculations for cross metathesis of -pinene with (Z)-3-methylpent-2-
ene with a second generation Grubbs catalyst [26]. [Ru3] can interact with methyl acrylate to
generate the self-metathesis products 3+4 (Fig. 3 (a)), and with -pinene, (Fig. 3 (b)), en route
to the expected cross metathesis product, which is however not formed experimentally. Route
(Fig. 3-(c)) is a non-productive pathway but constitutes nevertheless a pathway for the
formation of [Ru4]. [Ru4] can interact with methyl acrylate according to two
regioselectivities. Route (Fig. 3 (e)) is the non-productive reverse reaction of (Fig. 3-(c)) and
only route (Fig. 3 (d)) would give the expected product and this one also does not take place
experimentally. The productive interaction of [Ru4] with -pinene (Fig. 3-(f)) would lead to
the self-metathesis product but this reaction is unlikely and not observed as it was shown that
the less substituted methylenecyclohexane did not give self-metathesis, [27] and more
generally 1,1-disubstituted olefins were reluctant to self-metathesis with ruthenium catalysts
[28]. Thus, the sole productive reaction is the self-metathesis of methyl acrylate, which leads
to the formation of dimethyl fumarate and maleate (Fig. 3 (a)).

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Figure 3. Catalytic steps for the cross metathesis of -pinene 1 with methyl acrylate
The same carbenic species [Ru3] and [Ru4] are formed during the cross metathesis of
-pinene with dimethyl fumarate 3 and maleate 4 (Fig. 4). The interaction of [Ru3] with
maleate is responsible for the isomerization of the starting olefin into dimethyl fumarate 3
(Fig. 4 (a)). The route described in Fig. 4 (b) is the same as the one of Fig. 3 (b) that is not
operative using methyl acrylate. In Fig. 4, route (c) does not lead to cross metathesis product
and route (e) similar to Fig. 3 route (f) does not take place for steric reason. Finally, from 3 or
4 only routes Fig. 4 (b) and (d) would lead to the expected cross metathesis product 5. It is

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however difficult to conclude which one is the predominant or the sole one. Route (d)
represents a similar pathway as the one proposed by A.J. Robinson for the cross metathesis of
an excess of -pinene (30 equiv.) with isoprenyl olefins [17] and M.A. Tlenkopatchev for the
cross metathesis of stoichiometric amounts of -pinene and the less hindered
3-methylpent-2-ene [26] involving ruthenium carbene species such as [Ru4] arising from the
terpene. Even though the route described in Fig. 3 (b) is not productive from methyl acrylate,
the same pathway described in Fig. 4 (b) involving [Ru3] and -pinene might be productive
from dimethyl maleate 3 or fumarate 4. This might be the result of the competitive interaction
of [Ru3] with acrylates versus -pinene, which is much more favored with methyl acrylate
(Fig. 3 (a) vs Fig. 3 (b)), considering steric factors and the excess of methyl acrylate hence
leading preferentially to the self-metathesis products 3 and 4. The steric discrimination is
much less important between methyl fumarate or maleate versus -pinene as depicted in
ruthenacycle formation (Fig.4 (a) and (b)) thus making the productive formation of the cross-
metathesis product feasible. It must be noted that a similar competition between self-
metathesis versus cross metathesis of acrylate has previously been observed when an acrylate
and
a
moderately hindered gem-disubstituted olefins such as 2-methylheptene or
methylenecyclohexane were reacted in the presence of a second generation ruthenium catalyst
[25].

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Figure 4. Catalytic steps for the cross metathesis of -pinene 1 with dimethyl maleate 4
The comparison of the productive pathways in Fig. 3 and Fig. 4 reveals that with methyl
acrylate a ruthenium methylidene [Ru5] is formed, which then generates ethylene to restore
[Ru3] from methyl acrylate, and that on the other hand, Ru=CHCO2Me [Ru3] is generated in
the productive routes Fig.4 (a) and (d). The formation of [Ru5] is known to facilitate
decomposition of the catalyst [29], and the presence of ethylene has also been reported as
detrimental to some metathesis reactions, [30] which might contribute to explain the absence
of cross metathesis of -pinene 1 with methyl acrylate. It is also surprising that during the
reaction with methyl acrylate, the dimethyl maleate and fumarate, which are generated in situ
are not involved in further cross metathesis with -pinene. This observation suggests that the

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self-metathesis of methyl acrylate is much faster than the cross metathesis reaction with the
terpene and during this transformation after full consumption of methyl acrylate the amount
of active catalyst is decreased due to fast decomposition of the catalytic species at 100 °C.
The new products (E)-5 and (Z)-5 were produced in satisfactory yields but could not be
separated by column chromatography. A fine NMR analysis of their mixture based on
NOESY and HSQC experiments (see Supporting Information for details) together with data
from the literature on -pinene 1, [31,32] made possible the full characterization of each
stereoisomer. In particular, the stereochemistry was clarified by Nuclear Overhauser Effect
study, which revealed interaction between the ethylenic proton C(10)H (at 4.46 ppm) with the
C(1) H proton in the (E)-5 isomer (at 2.46 ppm), and interaction of the same ethylenic proton
C(10)H (at 5.60 ppm) with one of the proton of the methylene group at C(3) in the (Z)-5
isomer (at 2.21 ppm).
Using dimethyl fumarate 4 led to a slightly higher E/Z ratio as compared to dimethyl maleate
(average value E/Z= 71:29 from 4, and E/Z = 60:40 from 3). It is noteworthy that the
stereoselectivity in favour of the E-isomer is much less pronounced than that obtained with
less bulky linear terpenes [12].
Similarly, the cross metathesis of acrylonitrile with 1 did not lead to the cross metathesis
product but following the same principle, the symmetrical fumaronitrile 6 led to a mixture of
(E)-7 and (Z)-7 stereoisomers according to equation (2) (Figure 2). With this cross metathesis
partner, the conversion of -pinene 1 was much lower than starting from dimethyl fumarate 3
as in the best case a conversion of 32% (14% isolated yield) was obtained in DMC at 100 °C
for 15 h in the presence of 2.5 mol% of catalyst [Ru1] with a -pinene concentration of 0.37
mol/L. The structure of the stereoisomers has also been determined by NOE experiments and
the major stereoisomer was found to be the (E)-7 isomer, which contrasts with all previous
results reported with acrylonitrile where the (Z)-isomer is the major one.[11,33] Indeed,
interaction between the ethylenic proton C(10)H (at 4.95 ppm) with the C(1) H proton in the
(E)-7 isomer (at 2.58 ppm), and interactions of the same ethylenic proton C(10)H (at 5.04
ppm) with one of the protons of the methylene group at C(3) in the (Z)-7 isomer (at 2.40 and
2.70 ppm) were observed in the NOESY spectrum (see Supporting Information).
Then, we investigated the cross metathesis of -pinene 1 with the non-symmetrical methyl
crotonate 8 featuring an internal double bond (Figure 2 - (3)). In the presence of catalyst Ru2
(2.5 mol%), the cross metathesis reaction of 1 with a twofold excess of 8 took place in DMC

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([1]= 0.74 mol/L) at 100 °C leading to 66% conversion of -pinene but the reaction was not
selective and beside the functional derivatives 5 (E+Z), the purely aliphatic stereoisomers of
the -pinene derivative 9 were formed in a (9)/(5) molar ratio of 57:43 (1.3) as determined by
GC analysis of the crude reaction mixture. When the reaction was carried out without solvent
in the presence of 5 mol% of Ru2, 48% conversion of 1 was obtained and the (9)/(5) ratio
was much higher (6.25). As expected, (E)-5 was the major acrylic isomer but the (E)- and
(Z)-stereoisomers of 9 were not separated by GC and thus it was not possible to give the
corresponding stereoisomeric ratio.
2.2. Cross metathesis of acrylic olefins with limonene 2
With the less sterically constrained terpene 2, the reaction with methyl acrylate was also
inefficient and only dimethyl maleate 3 and fumarate 4 were formed as previously reported
[13]. However, the cross metathesis with the symmetrical maleate and fumarate in the
presence of 2.5-5 mol% of Ru1 and Ru2 was successful and produced the expected and new
acrylic stereoisomers of 10 according to equation (4) (Figure 5). Surprisingly, under the
conditions described above for -pinene 1 transformation, the productivities were generally
lower, but reasonable conversions of 60% could be obtained with a (E/Z)-10 ratio of 75:25
(Table 2 – see Supporting Information). The nature of the stereoisomers was also
1
unambiguously determined by H and 13C NMR. In the (E)-isomer 10, the acrylic proton at
C(9) (5.68 ppm) is in interaction with protons at C(3), C(4) and C(5), whereas in the (Z)-
isomer 10, the same proton at C(9) (5.64 ppm) is in interaction with the methyl proton at
C(10) (1.81 ppm) only. It can be noted that under the conditions of Table 2, entry 7, the
complexes Ru3 and Ru4 were also inactive.

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Figure 5. Cross metathesis of limonene with methyl fumarate, maleate and fumaronitrile
The nitrile derivatives 12 could also be formed upon reaction of limonene 2 with
fumaronitrile 11 but in the presence of 2.5 mol% of Ru1 at 100 °C for 15 h, a very low
isolated yield of 7% was obtained corresponding to a conversion of only 13% (Figure 5 -
equation (5)). In this case, the (Z)-12 isomer was obtained as the major product (Z/E= 86:14).
2.3. Cross metathesis of allylic olefins with -pinene 1 and limonene 2
Functional allylic esters and halides are suitable cross metathesis partners to introduce
functional groups to the purely aliphatic terpenes 1 and 2. Using this methodology, natural
products including unsaturated fatty esters, acyclic terpenes and lignin-derived allylbenzene
derivatives have been functionalized by cross metathesis with terminal olefinic partners such
as allyl acetate and allyl halides or 1,4-diacetoxybut-2-ene as internal olefin [10]. Again when
allyl acetate was used, no cross metathesis reaction took place with the terpenes 1 and 2. On
the other hand, the expected cross metathesis products 14 and 15 were formed in moderate
yields when cis-1,4-diacetoxybut-2-ene 13 was used (Figure 6). With this cross metathesis
partner, the (E)-isomers of 14 and 15 were formed as the major products (> 90% (E)-14, and
(Z)-15 was not detected by 1H NMR).

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Figure 6. Cross metathesis of -pinene 1 and limonene 2 with cis-1,4-diacetoxybut-2-ene 13
However, the efficiency of these metathesis reactions was much lower with this cross
metathesis partner than with acrylic esters. The influence of catalyst loading and substrates
ratio were weak and the best conversions reaching 30-40% of the terpene were obtained under
neat conditions (Table 3 – see Supporting Information).
2.4. Sequential cross metathesis/hydrogenation
It is now well established that the ruthenium residues resulting from olefin metathesis
transformations are catalysts for subsequent hydrogenation of the formed carbon-carbon
double bonds. This catalytic property, which was first used in metathesis polymerization
(ROMP and ADMET)/hydrogenation processes [34] has known further developments in
sequential cross metathesis/hydrogenation transformations [35]. We have shown that
performing first the cross metathesis reaction of -pinene 1 with dimethyl fumarate 4 in the
presence of 5 mol% of Ru2 as catalyst in DMC at 100 °C for 16 h and then applying a
hydrogen pressure of 40 bar at 80 °C during 8 h led to full conversion of the terpene into the
1
saturated ester 16 (see Supporting Information). H NMR analysis confirmed that the E and Z
isomers 5 disappeared and were hydrogenated into the same product 16 isolated in 40% yield.
3. Conclusion
The cross metathesis of sterically demanding gem-disubstituted olefins with terminal
functional olefins in the presence of ruthenium catalysts is known to be a challenging

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reaction. Based on a few observations from the literature, we have developed a strategy
involving more hindered symmetrical functional internal alkenes rather their terminal
metathesis equivalents as cross metathesis partners for cross metathesis with bulky terpenes.
Using Hoveyda-Grubbs type catalysts, it was thus possible to introduce ester and nitrile
functional group to -pinene 1 and limonene 2 via cross metathesis with dimethyl fumarate
and maleate, fumaronitrile and 1,4-diacetoxybut-2-ene under neat conditions or in dimethyl
carbonate as a green solvent without production of any byproduct. This cross metathesis
reaction provides a straightforward access to new bio-sourced products. Wider catalysts
screening involving the most recent ruthenium and molybdenum complexes might allow
improvement of the productivity of these transformations.
Acknowledgements
The authors acknowledge CAPES-COFECUB for support to the project no. PHC 884-17
(France) and 883/2017 (Brazil); D. M. also thanks projects CNPq 309570/2016-6, CNPq
422290/2016-5, FAPESP 2018/01258-5 and the Sustainable Technologies Unit of UFABC
(NuTS). Finally, L. S. F. thanks FAPESP 2015/26787-2 for the scholarship.
Author Contribution Statement
Luciana Sarmento Fernandes: experimental investigation, writing parts of the initial draft
Dalmo Mandelli: management of the project in Brazil, conceptualization
Wagner A. Carvalho: co-supervision in Brazil
Cédric Fischmeister: methodology, resources, preparation of published work, supervision
Christian Bruneau: conceptualization, project administration, funding acquisition, preparation of
published work,
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Declaration of interests
☒ The authors declare that they have no known competing financialinterests orpersonal
relationships thatcould have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:
Highlights
1. Olefin cross metathesis from sterically demanding natural terpenes
2. First evidence that fumarates and maleates are better cross metathesis partners than acrylates
-pinene and limonene