Methyl vinyl glycolate as a diverse platform molecule

Article abstract of DOI:10.1039/c6gc01556e

Methyl vinyl glycolate (methyl 2-hydroxybut-3-enoate, MVG) is available by zeolite catalyzed degradation of mono- and disaccharides and has the potential to become a renewable platform molecule for commercially relevant catalytic transformations. This is further illustrated here by the development of four reactions to afford industrially promising structures. Catalytic homo metathesis of MVG using Grubbs-type catalysts affords the crystalline dimer dimethyl (E)-2,5-dihydroxyhex-3-enedioate in excellent yield and with meso stereochemical configuration. Cross metathesis reactions between MVG and various long-chain terminal olefins give unsaturated α-hydroxy fatty acid methyl esters in good yields. [3,3]-Sigmatropic rearrangements of MVG also proceed in good yields to give unsaturated adipic acid derivatives. Finally, rearrangement of the allylic acetate of MVG proceeds in acceptable yield to afford methyl 4-acetoxycrotonate.

Full text of DOI:10.1039/c6gc01556e

View Article Online
View Journal
Green
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: R. Madsen, A.
Sølvhøj and E. Taarning, Green Chem., 2016, DOI: 10.1039/C6GC01556E.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/greenchem

Please do not adjust margins
Green Chemistry
Page 1 of 8
View Article Online
DOI: 10.1039/C6GC01556E
Journal Name
ARTICLE
Methyl Vinyl Glycolate as a Diverse Platform Molecule†
Amanda Sølvhøj,a,b Esben Taarningb and Robert Madsen*,a
Received 00th January 20xx,
Accepted 00th January 20xx
Methyl vinyl glycolate (methyl 2‐hydroxybut‐3‐enoate, MVG) is available by zeolite catalyzed degradation of mono‐ and
disaccharides and has the potential to become a renewable platform molecule for commercially relevant catalytic
transformations. This is further illustrated here by the development of four reactions to afford industrially promising
structures. Catalytic homo metathesis of MVG using Grubbs‐type catalysts affords the crystalline dimer dimethyl (E)‐2,5‐
dihydroxyhex‐3‐enedioate in excellent yield and with meso stereochemical configuration. Cross metathesis reactions
between MVG and various long‐chain terminal olefins give unsaturated ‐hydroxy fatty acid methyl esters in good yields.
[3,3]‐Sigmatropic rearrangements of MVG also proceed in good yields to give unsaturated adipic acid derivatives. Finally,
rearrangement of the allylic acetate of MVG proceeds in acceptable yield to afford methyl 4‐acetoxycrotonate.
DOI: 10.1039/x0xx00000x
www.rsc.org/
lactate from various mono‐ and disaccharides in methanol
solution.6 MVG is believed to be formed in a dehydration‐
esterification reaction catalyzed by the stannosilicate catalyst from
tetroses which are formed in low amounts from glucose in a retro‐
Introduction
Platform molecules, or base chemicals, are molecules which play a
central role in the infrastructure of the chemical industry, i.e.
intermediates which are used for the production of several other
chemical products.1 Conventional fossil‐derived platform molecules
include ethylene, propylene and benzene. In recent years, much
attention has been directed towards developing renewable
platform molecules.2 Some of the most important characteristics of
a future renewable platform molecule are that it can be produced
at low cost from biomass, and that it can be used for the production
of several other useful chemical products. Examples of potential
platform molecules which have been investigated previously
include ethanol, furfural and 5‐hydroxymethylfurfural. Ethanol has
been envisaged as a platform molecule for the production of
ethylene, ethyl acetate and acetic acid.3 Furfural has been
investigated as a platform molecule for the production of furan and
methyl tetrahydrofuran.4 Finally, 5‐hydroxymethylfurfural has been
investigated for the production of dimethyl furan, levulinic acid and
terephthalic acid.5
aldol reaction. A mechanistic study of the conversion of tetroses to
MVG and other ‐hydroxy acid derivatives confirms this
assumption.7 The theory is further substantiated by the fact that the
yield of MVG ranges from 3‐11% when employing pentoses or
hexoses as substrates,6 but when employing a tetrose as the
substrate the yield increases to 50‐56%.6,8 A subsequent study has
found that the yield of MVG from glucose can be further improved
to around 18% by the presence of alkali metal salts.9 Under these
reaction conditions the co‐product methyl lactate (ML) is obtained
in close to 50 % yield.9 The various sugars that can be used as feed
for the production of ML and MVG may be derived from 2nd
generation biomass like corn cobs. From one ton of corn cobs it is
possible to obtain about 265 kg of ML and 62 kg of MVG.6,9‐11
Although MVG fulfills the requirements for a good bio‐based
platform molecule, its applications are relatively unexplored. MVG
dimerizes under alkaline conditions via
a cascade reaction
commencing with the isomerization to methyl 2‐oxobutanoate
(Scheme 1). This isomer enolizes and undergoes an aldol
condensation and ultimately forms a cyclic dimer, which upon
heating decarboxylates to 5‐ethyl‐2‐hydroxy‐3‐methyl‐2‐furanone
(also known as maple furanone ‐ an important food‐flavoring
compound).12
Another interesting candidate as a future platform molecule is
methyl 2‐hydroxybut‐3‐enoate (methyl vinyl glycolate, MVG). It is a
small molecule with a simple structure, and yet it possesses several
functional groups, providing it with ample handles for many
different chemical transformations. It was first observed as a
byproduct in the stannosilicate catalyzed formation of methyl
a. Department of Chemistry, Technical University of Denmark
2800 Kgs. Lyngby, Denmark
E‐mail: rm@kemi.dtu.dk
b. Haldor Topsøe A/S
Haldor Topsøes Allé 1, 2800 Kgs. Lyngby, Denmark
Electronic Supplementary Information (ESI) available: NMR spectra with
†
assignments for all compounds (crystal structure in Fig. 2 is deposited at CCDC
1481046)
See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 1
Please do not adjust margins

Green Chemistry
Please do not adjust margins
Page 2 of 8
Journal Name
ARTICLE
Scheme 1 Previously reported transformations of MVG. a) Alkaline dimerization to
form “maple furanone”, 87%12, b) Radical addition of methanethiol to form the hydroxy
analog of methionine, 85%13, c) Claisen rearrangement to yield 6‐oxohex‐2‐enoates, 46‐
manipulation of the ‐hydroxy groups. A cross metathesis reaction
View Article Online
with long straight‐chain terminal olefinsDOwI:o1u0l.d103r9e/sCu6lGt Ci0n155th6Ee
formation of unsaturated ‐hydroxy fatty acid methyl esters
(FAME’s). These may be easily reduced to their saturated
counterparts, which are well known surfactants with a variety of
applications.25
64%14 and d) Zeolite catalyzed formation of the glycolide dimer, 16‐24%15
.
In the presence of a free radical initiator, like AIBN or NBS,
methanethiol adds to the double bond of MVG giving rise to methyl
2‐hydroxy‐4‐(methylthio)butanoate,13 which is the methyl ester of
the hydroxy analog of the α‐amino acid methionine. Both the amino
acid and its hydroxy analog are produced synthetically on a large
scale and used e.g. as a dietary supplement in poultry feed.
With acid catalysis the hydroxy group of MVG adds to various
aldehydes forming hemiacetals, which upon dehydration give rise
to allyl vinyl ethers. The latter rearrange in a Claisen [3,3]‐
sigmatropic shift to the corresponding 6‐oxohex‐2‐enoates.14 The
1,6‐dioxo compounds are interesting synthetic motifs particularly as
precursors to large scale polyester and polyamide monomers such
as adipic acid, caprolactone and caprolactam.
Recently the formation of a vinyl glycolide dimer from 2‐
hydroxybut‐3‐enoic acid has been achieved in up to 24% yield by
employing a shape selective zeolite catalyst.15 MVG has also been
copolymerized with lactic acid (LA) to tune the properties of PLA‐
based polymers. This can be done either by varying the ratio
between MVG and LA or through functionalization of the reactive
vinyl side chain of the MVG units.16
The allylic alcohol moiety of MVG makes it a precursor for various
allyl vinyl ethers and derivatives hereof, which may be rearranged
in a [3,3]‐sigmatropic shift yielding 1,6‐diesters or other 1,6‐dioxo
structures as products. These compounds may serve as direct
precursors for valuable polyester and polyamide monomers like
adipic acid, caprolactone or caprolactam. Finally, the secondary
allylic alcohol may be transformed into its primary allylic alcohol
isomer, i.e. a 1,4‐dioxygenated motif, which could serve as a
precursor for 1,4‐butanediol (BDO) or ‐butyrolactone (GBL). This
transformation may occur by acetylation of the allylic alcohol
followed by a rearrangement of the allylic acetate.
Herein, we emphasize the potential of MVG by describing several
new transformations of MVG into a range of industrially promising
structures by the use of homo and cross metathesis reactions as
well as Claisen and allylic alcohol rearrangements.
Results and discussion
Homo metathesis of MVG
Apart from these very product‐specific applications of MVG,
other examples include various functional group manipulations like
the Larock quinolone synthesis,17 the Heck reaction,18 the Tsuji‐
Trost reaction,19 olefin cross metathesis reactions,20 1,3‐dipolar
additions,21 reduction of the ester group22 and alkylations of the
alcohol.23
Although the examples are few in number, the reaction types are
versatile emphasizing that MVG is a molecule for which many
chemical transformations are possible. In the present work the focal
point was reactions that would transform MVG into industrially
important compounds either directly or through few and simple
manipulations. Four general strategies were devised, as outlined in
Scheme 2.
Preliminary experiments had shown that a solid precipitated when
heating MVG with a metathesis catalyst in the absence of a solvent.
The solid was identified as the homo metathesis product dimethyl
2,5‐dihydroxyhex‐3‐enedioate. Thus, a series of experiments were
performed in order to optimize the yield of the reaction (Table 1).
Comparison of Grubbs 1st and 2nd generation catalysts (Fig. 1)
showed that the 2nd generation catalyst was far superior to the 1st
generation complex both in terms of isolated yield and the amount
of catalyst. The 2nd generation catalyst gave an isolated yield of 75%
with a 0.4% loading of catalyst on a 10 mmol scale (entry 6),
whereas the 1st generation catalyst gave only 8% isolated yield with
a 5% loading on the same scale (entry 1).
The product is crystalline and the reaction mixture quickly
solidifies completely, as it is run without the presence of a solvent.
This hampers efficient stirring and may hinder full conversion.
Attempts to run the reaction in a solvent (toluene or ethyl acetate)
were less successful and resulted in a lowering of the yield (entries
2 – 5).
Scheme 2 Four general strategies for transformation of MVG into valuable compounds.
a) Homo metathesis of MVG to form a 1,6 diester. b) Cross metathesis of MVG to form
unsaturated ‐hydroxy FAME’s. c) Claisen‐type rearrangements to form 6‐oxo‐
substituted hex‐2‐enoic acid derivatives. d) Oxygen‐centered rearrangement to form 4‐
oxybut‐2‐enoic acid compounds.
Fig. 1 From left to right: Grubbs 1st generation catalyst, Grubbs 2nd generation catalyst
and Hoveyda‐Grubbs 2nd generation catalyst.
A homo metathesis reaction24 would yield a dimer of MVG, which
could be an interesting monomer for polyester production, due to
its 1,6‐diester skeleton which is reminiscent of adipic acid, and
because of the inherent possibility for further functionalization by
Increasing the scale of the reaction from 10 to 19 mmol (entry 7)
resulted in an increase of the yield from 75% to 85%. Further
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 2
Please do not adjust margins

Page 3 of 8
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
increasing the scale to 39 mmol gave a slight improvement of the crystallization, when employing the reaction conditions in entry 10,
View Article Online
DOI: 10.1039/C6GC01556E
yield to 88% (entry 8). The catalyst was then successfully exchanged Table 1. More of the product is available in the mother liquor, but
for the less expensive and more stable Hoveyda‐Grubbs 2nd must be purified by chromatography or collected in larger amounts
generation catalyst (Fig. 1) with an increase in yield as an additional in order to be isolated by a further crystallization.
bonus (entry 10). With only 0.4% catalyst loading on a 19 mmol
As can be seen from the reaction scheme in Table 1 the homo
scale the isolated yield reached 93%. The catalyst loading was metathesis reaction of MVG forms equimolar amounts of ethylene
subsequently reduced to 0.2% without any significant decrease in gas as a co‐product, which may easily be separated from the main
the yield (entry 11). A further reduction of the catalyst loading to product. This increases the amount of utilized carbon atoms in the
0.05% resulted in a noticeable lowering of the yield to 77% (entry reaction from 80 to 100 %, since ethylene is valuable as a bio‐based
12), although this seems in part to be overcome by a further monomer on its own.
upscaling of the reaction (entry 13).
The product has 2 stereocenters, corresponding to three
different stereoisomers, of which one is a meso form. Taking into
account the possibility of forming both the (E)‐ and the (Z)‐isomer,
the total number of different isomers amounts to six. Surprisingly,
the reaction yields only one isomeric form of the product, which
was determined by X‐ray diffraction to be the meso form of the (E)‐
isomer (Fig. 2). NMR spectra of the crude reaction mixture show no
signals from a (Z)‐double bond, and a GC of the crude reaction
mixture shows no presence of other diastereomeric forms. Most
likely, the high crystallinity of the meso (E)‐isomer is the main
driving force for the exclusive formation of this compound since the
metathesis reaction is a reversible transformation.
It should be noted that while all the reactions were run at 80 °C the
reaction mixture solidified already at 30 °C when employing the
Hoveyda‐Grubbs 2nd generation catalyst. With the Grubbs 2nd
generation catalyst immediate precipitation was first observed at
temperatures above 60 °C. All the reactions were run overnight (16
h), although complete solidification of the mixture seems to occur
within the first hour of the reaction.
Table 1 Optimization of the homo metathesis of MVGa
O
O
OH
O
H2C CH2
+
O
O
The dimer is a structurally interesting molecule for which many
applications can be envisioned. The 1,6‐diester structure is
reminiscent of adipic acid, making it reasonable to assume that the
MVG dimer can be utilized in similar applications. Unlike adipic acid
though, the metathesis dimer possesses two hydroxy substituents
which introduces the possibility of a functionalized polyester
monomer. In fact, very recently Sels and coworkers performed a
study where 2,5‐dihydroxyhex‐3‐enedioic acid (DHHDA) was
synthesized and copolymerized with lactic acid to yield a crosslinked
polyester, which showed improved thermal stability as compared to
pure PLA.26 Furthermore, DHHDA was also reacted with
hexamethylenediamine to give a partly bio‐based polyamide, which
in both structure and properties resembles the adipic acid‐based
polyamide nylon‐6,6.26 The meso form of the MVG dimer is achiral
but possesses two stereocenters, making both positions pro‐chiral.
This makes the molecule a potential precursor for asymmetric
synthesis.
OH
OH
O
Catalyst
Loading
(mol%)
Scaleb
(mmol)
Solvent &
vol.c
Yieldd
(%)
1e
2
Grubbs 1st gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
5
10
5
‐
8
0.3
0.3
0.3
2.2
0.4
0.4
0.4
0.4
‐
74
55
63
46g
75
85
88
73
3
2.5
5
toluene 1:1
4
toluene 2:1
5f
6
2.5
10
19
39
2.5
EtOAc 4:1
‐
‐
‐
‐
7
8
9
Hoveyda‐Grubbs
2nd gen.
10
11
12
13
a
Hoveyda‐Grubbs
0.4
0.2
19
19
20
39
‐
‐
‐
‐
93
90
77
80
2nd gen.
Hoveyda‐Grubbs
2nd gen.
Hoveyda‐Grubbs
0.05
0.045
2nd gen.
Hoveyda‐Grubbs
2nd gen.
The experiments were performed in a Schlenk flask under inert atmosphere at
80 °C. b Amount of MVG. c Ratio = volume solvent : MVG. d Isolated yield. e Reaction
temperature 40 °C. f Reaction temperature 70 °C. g GC yield.
Fig. 2 Crystal structure of dimethyl 2,5‐dihydroxyhex‐3‐enedioate. Only the meso‐form
of the (E)‐isomer is formed.
Cross metathesis of MVG
The crude product may be purified by direct crystallization from
ethyl acetate, which gave 71% yield of the pure product in the first
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 3
Please do not adjust margins

Green Chemistry
Please do not adjust margins
Page 4 of 8
Journal Name
ARTICLE
MVG can also be brought to react with long chain terminal olefins The solvent may be exchanged for ethyl acetate, but at the expense
View Article Online
in a cross metathesis reaction, yielding unsaturated ‐hydroxy of a significant reduction in the yield (40%, eDnOtrIy: 160)..1039/C6GC01556E
FAME’s. These can be hydrogenated to give their fully saturated
The reaction conditions are applicable to other olefinic
counterparts, which can be employed as surfactants either directly substrates. MVG was reacted with dec‐1‐ene to afford methyl (E)‐2‐
or after transformation into their alkali metal salts, sulfonates or hydroxydodec‐3‐enoate in 63% isolated yield (entry 7) and the
other derivatives. Bio‐based long chain terminal olefins can be same yield was obtained upon reaction with tetradec‐1‐ene to
obtained from unsaturated fatty acids, like oleic or linoleic acid afford methyl (E)‐2‐hydroxyhexadec‐3‐enoate (entry 8). In all cases
from palm oil, by reacting these with ethylene in a metathesis in Table 2, traces of the corresponding (Z)‐isomers of the cross
reaction.27 For optimization of the reaction conditions MVG was metathesis products were also detected, but the amounts were not
reacted with 1.5 equivalent of dodec‐1‐ene in refluxing further quantified.
dichloromethane under an inert atmosphere in the presence of a
In all the experiments, full conversion of the long chain terminal
suitable metathesis catalyst to afford methyl (E)‐2‐hydroxytetradec‐ olefin was achieved and formation of the corresponding internal
3‐enoate. The results are shown in Table 2.
alkene dimer was observed which accounts for the fate of the
excess olefin. This dimerization is faster than the cross metathesis
reaction, as expected for this type of substrate,28 but the dimer is
easily consumed in an ensuing cross metathesis reaction with MVG
and constitutes no hindrance for completion of the desired
reaction. The long chain alkene dimer is removed during the work‐
up and could in principle be reused as a substitute for the long
chain terminal olefin.
Table 2 Optimization of the cross metathesis reaction between MVG and a terminal
olefin
Catalyst
Loading
(mol%)
Olefin
Yielda
(%)
Yielda
Dimerb
(%)
[3,3]‐Sigmatropic rearrangements
c
Attaching a vinyl group to the allylic alcohol gives rise to a
substituted allyl vinyl ether which can rearrange in a [3,3]‐
sigmatropic shift as outlined in Scheme 3. One example is known
from the literature, namely the reaction between MVG and
diethoxyethane as shown in reaction a).14 In this case the resulting
trans‐acetal eliminates ethanol to yield the unsubstituted allyl vinyl
ether, which rearranges to afford methyl 6‐oxohex‐2‐enoate in 46%
yield.14
A similar reaction between MVG and an orthoacetate would give
a new orthoacetate, which upon elimination of an alcohol would
yield an alkoxy substituted allyl vinyl ether. Rearrangement of the
latter, known as a Johnson‐Claisen rearrangement,29 would then
lead to the formation of a diester of hex‐2‐enoic acid. Yet another
possible variation of this reaction, the Ireland‐Claisen
rearrangement,30 is based on the acylation of the allylic alcohol,
followed by formation of the corresponding silyl enol ether and
finally a [3,3]‐sigmatropic rearrangement leading to the free acid.
1
2
3
Grubbs 1st gen.
Grubbs 2nd gen.
5
5
5
dodec‐1‐ene
dodec‐1‐ene
dodec‐1‐ene
25
62
44
‐
c
‐
Hoveyda‐Grubbs
24
2nd gen.
4
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
Grubbs 2nd gen.
1
dodec‐1‐ene
dodec‐1‐ene
dodec‐1‐ene
dec‐1‐ene
68
65
40
63
63
19
14
5
0.5
1
c
6d
7
‐
1
21
20
8
1
tetradec‐1‐ene
a Isolated yield. b Dimer = dimethyl (E)‐2,5‐dihydroxyhex‐3‐enedioate. c Not isolated. d
With ethyl acetate as the solvent.
In analogy to the homo metathesis reaction, the Grubbs 2nd
generation catalyst proved to be far superior to the Grubbs 1st
generation complex. The former gave 62% isolated yield of methyl
(E)‐2‐hydroxytetradec‐3‐enoate (entry 2), whereas the latter gave
only 25% yield (entry 1). As for the homo metathesis reaction the
Hoveyda‐Grubbs 2nd generation catalyst seems to be more active,
and an intense development of ethylene gas was observed already
upon mixing the reagents with the catalyst at room temperature.
Regardless, the desired cross metathesis product was only isolated
in 44% yield (entry 3) and the byproduct from the homo metathesis
of MVG was isolated in 24% yield. Lowering the loading of Grubbs
2nd generation catalyst to 1 mol% while increasing the reaction time
to two days resulted in a slight increase of the yield to 68% (entry
4), while the yield of the byproduct was reduced to 19%. A further
lowering of the catalyst loading to 0.5 mol% gave a slight decrease
in the yield of the cross metathesis product (65%, entry 5), but also
resulted in a further reduction in the formation of the byproduct.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 4
Please do not adjust margins

Page 5 of 8
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
Scheme 3 Variations of the [3,3]‐sigmatropic rearrangement of vinylic derivatives of
MVG. a) Vinylation with CH3CH(OEt)2 and Claisen rearrangement affords methyl 6‐
oxohex‐2‐enoate as shown by Motherwell et al.14. b) Johnson‐Claisen rearrangement
with triethoxyacetate affords 6‐ethyl 1‐methyl hex‐2‐enedioate. c) Acetylation of MVG
followed by an Ireland‐Claisen rearrangement affords hex‐2‐enedioic acid.
View Article Online
DOI: 10.1039/C6GC01556E
Scheme 4 Rearrangement of allylic alcohol. a) AcCl, pyridine, CH2Cl2, 97% yield. b)
Pd(MeCN)2Cl2, THF, reflux, 59% yield.
The Johnson‐Claisen and the Ireland‐Claisen reaction were both
investigated with MVG. The most successful transformation was the
Johnson‐Claisen rearrangement. The reaction procedure is simple
and consists of heating MVG and the orthoacetate in the presence
of catalytic amounts of acetic acid. The temperature is kept just
below the boiling point of the orthoacetate until all MVG has been
converted, at which point the temperature is raised to 155 °C to
facilitate the rearrangement. A distillation column is attached
throughout the reaction, and the alcohol is continuously distilled
off, driving the reaction towards completion. In the reaction
between MVG and triethyl orthoacetate, the rearranged product 6‐
ethyl 1‐methyl (E)‐hex‐2‐enedioate was obtained in 74% isolated
yield. For the reaction between MVG and trimethyl orthoacetate
the yield was slightly lower and the product dimethyl (E)‐hex‐2‐
enedioate was obtained in 72% yield.
For the Ireland‐Claisen reaction the first step is the formation of
the acetate of MVG, which was formed by reacting MVG with acetyl
chloride. The acetylation gave a near quantitative yield in
dichloromethane while the product was obtained in 76% yield in
the more benign solvent ethyl acetate. The silyl enol ether of the
acetate of MVG was formed by treatment with LDA and TMSCl at
low temperatures. Subsequent heating to 90 °C in a sealed vessel
facilitated the rearrangement, and the silyl as well as the methyl
ester were cleaved off during workup, resulting in 66% isolated
yield of the free diacid.
While methyl 4‐acetoxybut‐2‐enoate may be an interesting
substrate on its own, the most direct application would arise by the
removal of the acetyl group to give methyl 4‐hydroxybut‐2‐enoate.
The latter may subsequently be reduced completely to 1,4‐
butanediol or partially reduced and cyclized to yield ‐
butyrolactone, both of them valuable large scale chemicals.
Conclusions
We have reported a range of new transformations of MVG into
industrially promising compounds utilizing either metathesis or
rearrangement reactions. The most successful reaction is the
dimerization of MVG to dimethyl (E)‐2,5‐dihydroxyhex‐3‐enedioate
by a homo metathesis reaction with the Hoveyda‐Grubbs 2nd
generation catalyst. This reaction proceeds in excellent yield to
afford the product as a single stereoisomer. Another metathesis
based transformation is the cross metathesis reactions of MVG with
long‐chain terminal olefins to give unsaturated ‐hydroxy FAME’s,
which may serve as precursors for a variety of surfactants.
Furthermore, two Claisen‐type rearrangements of MVG have been
developed and proven to work well. The products are unsaturated
derivatives of adipic acid, which are highly coveted as renewable
chemicals. Finally, rearrangement of the allylic alcohol of MVG has
been achieved through a palladium catalyzed transposition of the
acetate of MVG, yielding a 1,4‐dioxygenated motif, which may serve
as a precursor for chemicals like 1,4‐BDO or GBL. These results
show that MVG holds great promise as a novel renewable platform
molecule.
The Johnson‐Claisen reaction is performed in the absence of a
solvent with only a minuscule amount of acidic acid catalyst and
requires no distillation of the final product. The atom economy is
excellent since the alcohol from the orthoacetate is recovered
before the actual rearrangement. However, the temperature of the
transformation is rather high and the reaction time long for forming
the orthoacetate with MVG and achieving the rearrangement. The
Ireland‐Claisen reaction illustrates that the rearrangement can be
performed at a lower temperature and in a shorter time, but at the
expense of the atom economy.
Experimental section
General remarks: All solvents used were of HPLC grade, all
chemicals were bought from commercial suppliers. For dry column
vacuum chromatography (DCVC)32 was used Merck Silica Gel 60,
0.015—0.040 mm. Reactions were monitored by GC/MS on a
Shimadzu GCMS‐QP5000 instrument, which was also used for mass
spectrometry (data sets consist of mass and relative intensity). NMR
spectra were recorded on a Bruker Ascend 400 MHz instrument.
Chemical shifts were measured relative to the signals of residual
CHCl3 (H 7.26 ppm, C 77.16 ppm) or CD3OH (H 4.87 ppm, C 49.00
ppm) and are reported in ppm. HRMS data was obtained by
ultrahigh performance liquid chromatography high resolution mass
spectrometry (UHPLC‐HRMS) on a maXis G3 quadrupole time of
flight mass spectrometer (Bruker Daltronics, Bremen) equipped
with an electrospray (ESI) source. Melting points were recorded on
a Stuart SMP30 melting point apparatus and are uncorrected.
Allylic alcohol transposition
It is well known that palladium(II) complexes catalyze the
equilibration between the regioisomers of allylic acetates.31 This
also turned out to be the case for the acetate of MVG, which can be
rearranged into the isomer methyl 4‐acetoxybut‐2‐enoate with
catalytic amounts of palladium(II) species (Scheme 4). The best
results were obtained by treating the MVG acetate with catalytic
amounts of Pd(MeCN)2Cl2 in refluxing dry THF under nitrogen. The
reaction was monitored by GC/MS and showed full conversion of
the starting material to give the rearranged product in 59% isolated
yield.
Dimethyl
(2R,5S,E)‐2,5‐dihydroxyhex‐3‐enedioate:
Hoveyda‐
Grubbs 2nd generation catalyst (0.051 g, 0.08 mmol; 0.4 mol%) was
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 5
Please do not adjust margins

Green Chemistry
Please do not adjust margins
Page 6 of 8
Journal Name
ARTICLE
placed in a Schlenk flask, which was evacuated and purged with procedure as described above for methyl (E)‐2‐hydroxytetradec‐3‐
View Article Online
nitrogen three times. MVG (2.25 g, 19.3 mmol) was added to the enoate. Isolated yield: 0.888 g, 3.1 mmol; 63D%O.I: 10.1039/C6GC01556E
flask using a syringe. The reaction mixture was heated to 80 °C for 1H NMR (400 MHz, CDCl3):  5.89–5.77 (m, 1H), 5.46 (dd, J = 15.3,
18 h under a nitrogen atmosphere after which time it had turned 6.1 Hz, 1H), 4.57 (d, J = 6.0 Hz, 1H), 3.74 (s, 3H), 3.11 (s, br, 1H), 2.01
into a white solid. The crystals were crushed and washed with ethyl (q, J = 7.0 Hz, 2H), 1.39–1.30 (m, 2H), 1.22 (s, 18H), 0.84 (t, J = 6.6
acetate until colorless. The wash solvent was adsorbed onto a Celite Hz, 3H). 13C NMR (101 MHz, CDCl3):  174.29, 134.85, 126.02, 77.16,
support and purified by DCVC, eluting from heptane to ethyl 71.48, 52.63, 32.20, 31.97, 29.74, 29.71, 29.70, 29.66, 29.52, 29.41,
acetate, 10% increments, yielding more of the dimer as a colorless 29.20, 28.89, 22.73, 14.12. MS: m/z 284 (0.2) [M+], 225 (32), 123
solid. Combined yield: 1.83 g, 8.9 mmol; 93%.
(15), 111 (16), 109 (35), 97 (17), 95 (59), 83 (35), 81 (48), 71 (16), 70
1H NMR (400 MHz, CD3OD):  6.04 (d, J = 2.4 Hz, 2H), 4.74 (d, J = 2.3 (20), 69 (47), 67 (30), 57 (100), 55 (42), 43 (48), 41 (46). HRMS calcd.
Hz, 2H), 3.76 (s, 6H). 13C NMR (101 MHz, CD3OD):  174.3, 130.4, for C17H32O3Na [MNa+]: 307.2244, found: 307.2253; for C17H32O3K
71.9, 52.7. MS: m/z 205 (0.03) [MH+] 145 (11), 127 (44), 113 (12), 85 [MK+]: 323.1983, found: 323.1995.
(100), 59 (28), 57 (60), 55 (18). M.p. 129.7‐131.2 °C (recrystallized
from ethyl acetate). Crystal data from single‐crystal diffraction 6‐Ethyl 1‐methyl (E)‐hex‐2‐enedioate: MVG (0.918 g, 7.9 mmol)
studies for dimethyl (2R,5S,E)‐2,5‐dihydroxyhex‐3‐enedioate. and triethyl orthoacetate (1.973 g, 12 mmol) were placed in a 5 mL
C8H12O6, space group P 21/c, colorless, a = 7.8642(8) Å, b = round bottomed flask. Acetic acid (14 µL) was added and the flask
4.0675(3) Å, c = 14.5155(13) Å, V = 460.958 Å3, T = 120 K, Z = 2, Rint was equipped with a distillation column and the reaction mixture
= 0.0553.
heated to 140 °C with stirring for 21 h during which time ethanol
distilled off. The temperature was then raised to 155 °C for 7 h. The
Methyl (E)‐2‐hydroxytetradec‐3‐enoate: Grubbs 2nd generation mixture was allowed to cool to r.t., then water (2 mL) was added,
catalyst (0.045 g, 0.05 mmol; 1.1 mol%) was placed in a Schlenk and the solution extracted with Et2O (total volume 20 mL). The
flask and evacuated and purged with nitrogen three times. MVG combined organic phases were stirred with 1 M HCl (~15 mL) for 2
(0.577 g, 4.97 mmol) and dodec‐1‐ene (1.234 g, 7.33 mmol) were h, then the phases were separated and the organic phase washed
dissolved in CH2Cl2 (2 mL) and transferred to the flask via a syringe. with water (two times) and brine (two times), dried over Na2SO4,
The reaction mixture was heated to 40 °C with stirring under a filtered and concentrated in vacuo to yield the crude product as a
nitrogen atmosphere for 42 h. The solution was cooled down, pale yellow oil. Yield: 1.087 g, 5.8 mmol; 74%.
concentrated in vacuo on a Celite support and purified by DCVC, 1H NMR (400 MHz, CDCl3):  6.87 (dt, J = 15.7, 6.4 Hz, 1H), 5.78 (dt, J
eluting from heptane to ethyl acetate, 2% increments, to yield the = 15.6, 1.5 Hz, 1H), 4.06 (q, J = 7.1 Hz, 2H), 3.64 (s, 3H), 2.49–2.35
product as a yellow oil (0.866 g, 3.38 mmol; 68%).
(m, 4H), 1.17 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3):  172.1,
1H NMR (400 MHz, CDCl3):  5.81 (dtd, J = 15.1, 6.8, 1.3 Hz, 1H), 5.43 166.7, 147.0, 121.8, 60.6, 51.4, 32.4, 27.2, 14.1. MS: m/z 186 (0.1)
(ddt, J = 15.3, 6.2, 1.4 Hz, 1H), 4.54 (t, J = 5.0 Hz, 1H), 3.72 (s, 3H), [M+], 154 (32), 140 (29), 109 (45), 108 (100), 81 (58), 71 (26), 55
2.94 (d, J = 5.5 Hz, 1H), 1.99 (q, J = 7.0 Hz, 2H), 1.34–1.27 (m, 2H), (27), 53 (31). The observed chemical shifts are in accordance with
1.19 (s, 14H), 0.81 (t, J = 6.8 Hz, 3H). 13C NMR (101 MHz, CDCl3):  the literature values.33
174.4, 135.1, 126.0, 71.6, 52.8, 32.2, 32.0, 29.7, 29.7, 29.6, 29.4,
29.2, 28.9, 22.8, 14.2. MS: m/z 256 (0.1) [M+], 197 (30), 109 (34), 95 1,6‐Dimethyl (E)‐hex‐2‐enedioate: MVG (1.106 g, 9.5 mmol) and
(61), 81 (42), 67 (25), 57 (100), 55 (43), 43 (31), 41 (31). HRMS calcd. trimethyl orthoacetate (1.259 g, 10.5 mmol) were placed in a 5 mL
for C15H29O3 [MH+]: 257.2111, found: 257.2108. For C15H28O3Na round bottomed flask. Acetic acid (10.8 mg, 0.18 mmol) was added
[MNa+]: 279.1931, found: 279.1929.
and the flask was equipped with a distillation column and the
reaction mixture heated with stirring to 105 °C for 46 h during
Methyl (E)‐2‐hydroxydodec‐3‐enoate: Grubbs 2nd generation which time methanol distilled off. The temperature was then raised
catalyst (0.042 g, 0.05 mmol; 1 mol%), MVG (0.552 g, 4.75 mmol) to 155 °C for 7 h. The mixture was allowed to cool down to r.t., then
and dec‐1‐ene (1.042 g, 7.43 mmol) were reacted by the same the solution was stirred with 1 M HCl (~15 mL) and Et2O for 2 h, the
procedure as described above for methyl (E)‐2‐hydroxytetradec‐3‐ phases were separated and the organic phase washed with water
enoate. Isolated yield: 0.687 g, 3.01 mmol; 63%.
(two times) and brine (two times), dried over Na2SO4, filtered and
1H NMR (400 MHz, CDCl3):  5.90–5.79 (m, 1H), 5.47 (dd, J = 15.4, concentrated in vacuo to yield the crude product as a pale yellow
6.1 Hz, 1H), 4.58 (d, J = 6.1 Hz, 1H), 3.76 (s, 3H), 3.00 (s, br, 1H), 2.03 oil. Yield: 1.188 g, 6.9 mmol; 72%.
(q, J = 7.0 Hz, 2H), 1.39–1.32 (m, 2H), 1.23 (s, 10H), 0.85 (t, J = 6.7 1H NMR (400 MHz, CDCl3):  6.89 (dt, J = 15.7, 6.4 Hz, 1H), 5.80 (dt, J
Hz, 3H). 13C NMR (101 MHz, CDCl3):  174.35, 135.01, 126.01, 71.52, = 15.6, 1.5 Hz, 1H), 3.66 (s, 3H), 3.63 (s, 3H), 2.51–2.39 (m, 4H). 13
C
52.74, 32.22, 31.94, 29.48, 29.33, 29.21, 28.90, 22.73, 14.14. MS: NMR (101 MHz, CDCl3):  172.7, 166.8, 146.9, 121.9, 51.8, 51.5,
m/z 228 (0.1) [M+], 169 (34), 109 (25), 95 (75), 83 (19), 81 (43), 71 32.2, 27.2. MS: m/z 173 (0.2) [MH+], 141 (34), 140 (84), 113 (26),
(13), 70 (12), 69 (29), 67 (27), 57 (100), 55 (35), 43 (31), 41 (41). 112 (24), 111 (16), 109 (41), 108 (100), 97 (16), 85 (11), 82 (20), 81
HRMS calcd. for C13H24O3Na [MNa+]: 251.1618, found: 251.1624.
(87), 80 (24), 71 (68), 68 (10), 59 (52), 55 (24), 54 (14), 53 (59), 43
(11), 42 (12), 41 (36). The observed chemical shifts are in
Methyl (E)‐2‐hydroxyhexadec‐3‐enoate: Grubbs 2nd generation accordance with the literature values.34
catalyst (0.041 g, 0.05 mmol; 1 mol%), MVG (0.580 g, 4.99 mmol)
and tetradec‐1‐ene (1.450 g, 7.38 mmol) were reacted by the same Methyl 2‐acetoxybut‐3‐enoate: MVG (5.804 g, 50 mmol) and
pyridine (3.961 g, 50 mmol) were mixed with dry CH2Cl2 (170 mL)
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 6
Please do not adjust margins

Page 7 of 8
Green Chemistry
Please do not adjust margins
Journal Name
ARTICLE
and degassed with argon. Acetyl chloride (14.5 mL, 16.0 g, 204
mmol) was added dropwise via syringe (syringe pump at 3 mL/h)
and the reaction mixture stirred at r.t. overnight. The mixture was
poured into ice water and extracted with CH2Cl2. The combined
organic phases were washed with 1 M HCl, water and brine, dried
over anhydrous Na2SO4, filtered and concentrated in vacuo to yield
the crude product as a colorless oil (7.6 g, 48 mmol; 96%).
Acknowledgements
We thank the Innovation Fund Denmark and Haldor Topsøe A/S for
financial support.
View Article Online
DOI: 10.1039/C6GC01556E
Notes and references
1
T. J. Farmer and M. Mascal in Introduction to Chemicals from
Biomass, 2nd Ed. (Eds.: J. Clark, F. Deswarte), John Wiley &
sons Ltd., 2015, pp. 89–155.
P. N. R. Vennestrøm, C. M. Osmundsen, C. H. Christensen
and E. Taarning, Angew. Chem. Int. Ed., 2011, 50, 10502–
10509.
1H NMR (400 MHz, CDCl3):  5.90 (ddd, J = 16.9, 10.5, 6.3 Hz, 1H),
5.50–5.46 (m, 1H), 5.45–5.41 (m, 1H), 5.36–5.29 (m, 1H), 3.71 (s,
3H), 2.12 (s, 3H). 13C NMR (101 MHz, CDCl3):  170.0, 168.9, 130.0,
119.8, 73.0, 52.6, 20.6. MS: m/z 159 (0.1) [MH+], 116 (8), 99 (21), 43
(100). HRMS calcd. for C7H11O4 [MH+]: 159.0652, found: 159.0652.
For C7H10O4Na [MNa+]: 181.0471, found: 181.0471.
2
3
4
J. Sun and Y. Wang, ACS Catal., 2014,
(a) R. Mariscal, P. Maireles‐Torres, M. Ojeda, I. Sádaba and
M. López Granados, Energy Environ. Sci., 2016, , 1144–
4, 1078–1090.
9
(E)‐Hex‐2‐enedioic acid: In an oven‐dried 50 mL ace‐vial equipped
with a septum and an argon inlet was placed dry THF (4 mL). The
flask was cooled to ‐78 °C and n‐BuLi (2.0 M in hexanes; 3.85 mL,
7.7 mmol) was added via a syringe. The reaction was stirred for a
few minutes before diisopropylamine (1.5 mL, 10.5 mmol) was
added slowly via a syringe. After complete addition the cooling bath
was replaced with an ice‐water bath and the reaction was stirred
for 10 min at 0 °C before it was cooled down to ‐78 °C again. TMSCl
(0.978 mL, 7.7 mmol) was added via syringe. Methyl 2‐acetoxybut‐
3‐enoate (1.113 g, 7.0 mmol) in dry THF (2 mL) was added dropwise
with a syringe pump at a rate of 4 mL/h. After complete addition
the reaction was stirred at ‐78 °C for 5 min, then the cooling bath
was removed and the reaction allowed to warm up to r.t.
spontaneously. The vial was sealed and heated to 90 °C for 2 h.
The reaction was allowed to cool down to r.t., then the mixture was
treated with 15% (w/w) NaOH (20 mL) and washed with diethyl
ether (2 x 20 mL) and the aqueous phase acidified with
concentrated HCl while cooling in an ice bath. The solution was
evaporated to dryness on a rotary evaporator and the residue
extracted with Et2O. The organic phase was dried over Na2SO4,
filtered and concentrated in vacuo to yield the crude product as a
yellow solid. Yield: 0.6748 g, 4.7 mmol; 66%. Recrystallized from
heptane/ethyl acetate. M.p. 162.2‐163.2 °C (lit. 166‐167 °C).35
1H NMR (400 MHz, CD3OD):  6.96 (dt, J = 15.5, 6.4 Hz, 1H), 5.88–
5.79 (m, 1H), 2.53–2.44 (m, 4H). 13C NMR (101 MHz, CD3OD): 
176.1, 169.8, 149.1, 123.2, 33.2, 28.3.
1189; (b) K. Yan, G. Wu, T. Lafleur and C. Jarvis, Renew.
Sustain. Energy Rev., 2014, 38, 663–676.
5
6
(a) A. J. Kumalaputri, G. Bottari, P. M. Erne, H. J. Heeres and
K. Barta, ChemSusChem, 2014, 7, 2266–2275; (b) X. Hu, R. J.
M. Westerhof, L. Wu, D. Dong and C.‐Z. Li, Green Chem.,
2015, 17, 219–224; (c) J. J. Pachecho, J. A. Labinger, A. L.
Sessions and M. E. Davis, ACS Catal., 2015, 5, 5904–5913.
(a) M. S. Holm, S. Saravanamurugan and E. Taarning, Science,
2010, 328, 602–605; (b) M. S. Holm, Y. J. Pagán‐Torres, S.
Saravanamurugan, A. Riisager, J. A. Dumesic and E. Taarning,
Green Chem., 2012, 14, 702–706.
7
8
M. Dusselier, P. Van Wouwe, F. de Clippel, J. Dijkmans, D. W.
Gammon and B. F. Sels, ChemCatChem, 2013, 5, 569–575.
R. De Clercq, M. Dusselier, C. Christiaens, J. Dijkmans, R. I.
Iacobescu, Y. Pontikes and B. F. Sels, ACS Catal., 2015, 5,
5803–5811.
9
S. Tolborg, S. Meier, I. Sádaba, S. G. Elliot, S. K. Kristensen, S.
Shunmugavel, A. Riisager, P. Fristrup, T. Skrydstrup and E.
Taarning, Green Chem., 2016, 18, 3360–3369.
10 Y. D. Hang and E. E. Woodams, Lebensm. Wiss. Technol.,
2001, 34, 140–142.
11 See supplementary information for full calculation.
12 H. Stach, W. Huggenberg and M. Hesse, Helv. Chim. Acta,
1987, 70, 369–374.
13 K. E. Koenig, WO 9832735 A1, 1998.
14 (a) M. Freiría, A. J. Whitehead and W. B. Motherwell, Synlett,
2003, 805–808; (b) M. Freiría, A. J. Whitehead, D. A. Tocher
and W. B. Motherwell, Tetrahedron, 2004, 60, 2673–2692.
15 M. Dusselier, P. Van Wouwe, A. Dewaele, P. A. Jacobs and B.
F. Sels, Science, 2015, 349, 78–80.
16 M. Dusselier, P. Van Wouwe, S. De Smet, R. De Clercq, L.
Verbelen, P. Van Puyvelde, F. E. Du Prez and B. F. Sels, ACS
Catal., 2013, 3, 1786–1800.
17 M. T. Stone, Org. Lett., 2011, 13, 2326–2329.
18 (a) T. Terasaka, K. Nakamura, N. Seki, M. Kuno, S. Tsujimoto,
A. Sato, I. Nakanishi, T. Kinoshita, N. Nishio, H. Okumura and
K. Tsuji, WO 00/05217, 2000; (b) F. Sakai, N. Seki, Y. Tenda,
H. Yamazaki, C. Miyamoto, M. Kuno, H. Okumura and K.
Nakamura, WO 01/26605 A2, 2001.
Methyl (E)‐4‐acetoxybut‐2‐enoate: In a Schlenk flask was placed
Pd(MeCN)2Cl2 (0.095 g, 0.37 mmol; 18 mol%) and a magnetic
stirbar. The flask was evacuated and purged with nitrogen several
times. Methyl 2‐acetoxybut‐3‐enoate (0.324 g, 2.1 mmol) was
dissolved in dry THF (3.5 mL) and added to the Schlenk flask with a
syringe. The reaction was heated to reflux for 19 h under nitrogen.
The mixture was cooled down to r.t., adsorbed onto Celite and
purified by DCVC (eluting from heptane to ethyl acetate, 4%
increments) to yield the product as a colorless oil. Yield: 0.195 g, 1.2
mmol; 59%.
19 V. I. Ognyanov and M. Hesse, Synthesis, 1985, 645–647.
20 (a) M. A. Boudreau and J. C. Vederas, Org. Biomol. Chem.,
2007,
5, 627–635; (b) W. P. Unsworth, K. Stevens, S. G.
Lamont and J. Robertson, Chem. Commun., 2011, 47, 7659–
7661.
1H NMR (400 MHz, CDCl3):  6.85 (dt, J = 15.8, 4.6 Hz, 1H), 5.94 (dt, J
= 15.8, 2.0 Hz, 1H), 4.65 (dd, J = 4.6, 2.0 Hz, 2H), 3.65 (s, 3H), 2.02 (s,
3H). 13C NMR (101 MHz, CDCl3):  170.1, 166.1, 141.4, 121.7, 62.4,
51.6, 20.6. MS: m/z 116 (19) [MH‐Ac+], 99 (23), 87 (13), 85 (23), 84
(11), 55 (15), 43 (100). The observed chemical shifts are in
accordance with the literature values.36
21 J. Chanet‐Ray, M. O. Charmier‐Januario, R. Vessière and M.
Zucarelli, J. Heterocyclic Chem., 1994, 31, 1667–1671.
22 A. J. Pierik, T. Graf, L. Pemberton, B. T. Golding and J. Rétey,
ChemBioChem, 2008, 9, 2268–2275.
23 N. Lebrasseur, G.‐J. Fan, M. Oxoby, M. A. Looney and S.
Quideau, Tetrahedron, 2005, 61, 1551–1562.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 7
Please do not adjust margins

Green Chemistry
Please do not adjust margins
Page 8 of 8
Journal Name
ARTICLE
24 For a recent review on industrial applications of olefin
metathesis, see: C. S. Higman, J. A. M. Lummiss and D. E.
Fogg, Angew. Chem. Int. Ed., 2016, 55, 3552–3565.
View Article Online
DOI: 10.1039/C6GC01556E
25 (a) R. Pettigrew and P. Tissington, 3822222, 1974; (b) T.
Koizumi and H. Matsuzawa, 4802999, 1989; (c) A. A. El‐Sawy,
S. A. Essawy, M. M. El‐Sukkary and A. M. F. Eissa, Hung. J.
Ind. Chem., 1992, 20, 25–28; (d) R. J. Yu and E. J. Van Scott,
WO 96/40047, 1996.
26 A. Dewaele, L. Meerten, L. Verbelen, S. Eyley, W. Thielemans,
P. Van Puyvelde, M. Dusselier and B. Sels, ACS Sustainable
Chem. Eng., 2016, 4, DOI: 10.1021/acssuschemeng.6b00807.
27 T. W. Abraham, H. Kaido, C. W. Lee, R. L. Pederson, Y.
Schrodi and M. J. Tupy, US 20090264672 A1, 2009.
28 A. K. Chatterjee, T.‐L. Choi, D. P. Sanders and R. H. Grubbs, J.
Am. Chem. Soc., 2003, 125, 11360–11370.
29 W. S. Johnson, L. Werthemann, W. R. Bartlett, T. J.
Brocksom, T. Li, J. Faulkner and M. R. Petersen, J. Am. Chem.
Soc., 1970, 92, 741–743.
30 R. E. Ireland and R. H. Mueller, J. Am. Chem. Soc., 1972, 94
,
5897–5898.
31 L. E. Overman and F. M. Knoll, Tetrahedron Lett., 1979, 20
,
321–324.
32 D. S. Pedersen and C. Rosenbohm, Synthesis, 2001, 2431–
2434.
33 J. Y. Lee and S. Kim, Synlett, 2008, 49–54.
34 E. Hauptman, S. Sabo‐Etienne, P. S. White, M. Brookhart, J.
M. Garner, P. J. Fagan and J. C. Calabrese, J. Am. Chem. Soc.,
1994, 116, 8038–8060.
35 M. Viscontini and H. Köhler, Helv. Chim. Acta, 1954, 37, 41–
45.
36 R. V. Hoffman and B. S. Severns, J. Org. Chem., 1996, 61
,
5567–5573.
Table of Contents entry
Methyl vinyl glycolate (MVG) is available by zeolite catalyzed
degradation of sugars and constitutes a precursor to industrially
promising structures by homo metathesis, cross metathesis,
Claisen‐type rearrangements and allylic alcohol transposition.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 8
Please do not adjust margins