MINIREVIEW
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MINIREVIEW
Frontispiece picture:

Synthetic ..

.. diversity

MINIREVIEW
Catalytic Transformations of Functionalized Cyclic Organic
Carbonates
Wusheng Guo,*[a] José Enrique Gómez,[b][c] Àlex Cristòfol,[b][c] Jianing Xie,[b][c] and Arjan W. Kleij*[b][d]

Functionalized cyclic organic carbonates and related
heterocycles have emerged as highly versatile heterocyclic
substrates for ring-opening and decarboxylative catalytic
transformations allowing for the development of new stereoand enantioselective C‒N, C‒O, C‒C, C-S and C‒B bond
formation reactions. Transition metal mediated conversions
have only recently been rejuvenated as powerful approaches
towards the preparation of more complex molecules. This
minireview will highlight the potential of cyclic carbonates and
structurally related heterocycles with a focus on their synthetic
value and the mechanistic manifolds that are involved upon
their conversion.

research teams communicated on new metal- and organocatalyst based strategies focusing on the synthesis of more
elaborate and challenging compounds from both epoxides and
oxetanes.[8] More recently, also epoxy alcohols have shown to
offer new potential to construct more complex and functional
cyclic carbonates[9] through substrate controlled catalytic
approaches that complement the benchmark coupling reactions
between oxiranes and CO2.

cyclic organic carbonates  decarboxylative couplings 
heterocycles  homogeneous catalysis  transition metal catalysis

1. Introduction
Recycling of carbon dioxide into value-added organic molecules
and materials has received widespread attention among the
chemical communities.[1] Among the most studied transformations
that take advantage of the cheap, accessible and renewable
nature of CO2 as a carbon feedstock is its [3+2] cycloaddition
reaction with oxiranes affording cyclic organic carbonates. [2]
These oxygen-containing heterocycles have a long history, and
the development of new, more sustainable synthetic approaches
and applications has been an ongoing endeavor. [3] Whereas
conventionally these heterocyclic scaffolds found use as nonprotic solvents,[4] precursors to polycarbonates and related
polymers,[5] electrolytes[6] and as intermediates towards
commodity chemicals such as ethylene glycol,[7] recent trends
show a paradigmatic shift to their use as starting materials for
more complex organic targets.
Of vital importance to the exploration of post-synthetic
transformations that involve cyclic carbonates is the presence of
suitable functionality. In this regard, in the last decade several

[a]

[b]

[c]
[d]

Prof. Dr. W. Guo, Center for Organic Chemistry, Frontier Institute of
Science and Technology (FIST), Xi’an Jiaotong University, Xi’an
710045, China
J. E. Gómez, À. Cristòfol, J. Xie, Prof. Dr. A. W. Kleij, Institute of
Chemical Research of Catalonia (ICIQ), the Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007,
Tarragona, Spain
Universitat Rovira i Virgili, Departament de Química Analítica i
Química Orgànica, c/Marcel·lí Domingo, 1, 43007 Tarragona, Spain
Prof. Dr. A. W. Kleij
Catalan Institute of Research and Advanced Studies (ICREA), Pg.
Lluís Companys 23, 08010 Barcelona, Spain
E-mail: wusheng.guo@mail.xjtu.edu.cn; akleij@iciq.es

Figure 1. A naturally occurring cyclic carbonate (Hololeucin, top), examples of
synthetic cyclic carbonates (middle) and key functionalities for transition metal
mediated transformation of these versatile heterocycles (below).

Highly substituted cyclic carbonate rings are frequently
encountered in natural compounds, for example in Hololeucin
(see Figure 1). A comprehensive review describing the different
types of natural organic carbonates, and their biological origin and
properties was recently disclosed by Yue and co-workers.[10] The
advances made in synthetic cyclic carbonate chemistry have
allowed to (partially) mimic the structural complexity of biologically

MINIREVIEW
occurring cyclic carbonates. Additionally, the significant progress
in the preparation of these heterocycles also has provided easy
access to synthetically useful vinyl- and alkyne-based cyclic
carbonates (Figure 1, below). These specific carbonate examples
have enabled new transformations that go beyond classical
organic synthesis using cyclic carbonates as substrates. The
vinyl-substituted cyclic carbonates (VCCs) can be regarded as
allylic surrogates upon decarboxylation, and as such provide
reactive intermediates for Tsuji-Trost alkylations,[11] whereas the
alkynyl carbonates should facilitate an easy entry into propargylic
substitution chemistry.[12]
This minireview will present the latest developments,
discoveries and opportunities that have arisen in the area of
decarboxylative functionalization of mostly cyclic carbonates
using predominantly transition metal catalysis. As a prelude to this,
the review will first summarize catalytic ring-opening chemistry of
various cyclic carbonates resulting in valuable carbamate
products.

substrate was proposed to be the key factor for selective CO
bond scission.

Scheme 1. Aminolysis of cyclic carbonates by alkyl amines (path a) and
formation of a complex reaction mixture (below) using aniline and propylene
carbonate as reagents (path b).

2. Carbamates via Ring-Opening Chemistry
Since the first preparation of ethyl carbamate in 1845 by
Wohler,[13] carbamates have become highly interesting synthetic
targets due to their wide application as important starting
materials
of
polyurethanes,
agrochemicals
and
pharmaceuticals.[14] Traditionally carbamates are prepared from
phosgene, carbamoyl chloride or isocyanates, which has been
well documented.[15]
Ring opening of cyclic carbonates by amines represents a
straightforward and ecofriendly method toward carbamate
formation. The aminolysis of cyclic carbonates with alkyl amines
to deliver alkyl carbamates/urethanes typically occurs at room
temperature without the need for a catalyst,[16] while these
reactions generally proceed with poor regio-selectivity giving rise
to a mixture of two regioisomers (Scheme 1, path a). In sharp
contrast, the use of poorly nucleophilic aryl amines toward the
formation of N-aryl carbamate products is quite challenging. Selva
et al. reported that, in the presence of an ionic liquid catalyst, the
reaction between propylene carbonate and aniline requires very
high temperature (>140 oC) resulting in a complex reaction
mixture and, importantly, without any linear carbamate product
noted (Scheme 1, path b).[17]
The Kleij group recently reported the formation of N-aryl
carbamates from aryl amines and cyclic carbonates under
ambient
conditions
in
the
presence
of
1,5,7triazabicyclo[4.4.0]dec-5-ene (TBD) as organocatalyst, and most
of the reactions could be performed under solvent-free conditions
(Scheme 2, path a).[18] The N-aryl carbamate products are
potentially useful precursors for N-aryl isocyanates, which are
used on a large scale in the production of polyurethanes. [14a] DFT
calculations revealed a proton-relay mechanism based on a
hydrogen bonding activation by TBD (Scheme 2, below).[18]
Interestingly, this proton-relay system proved to be feasible for the
regioselective aminolysis of di- or trisubstituted cyclic carbonates
with alkyl amines (Scheme 2, path b).[19] Control experiments
suggested that the use of TBD catalyst is crucial for achieving
high regioselectivity. The steric demand in the cyclic carbonate

Scheme 2. TBD-catalyzed regioselective aminolysis of cyclic carbonates (path
a), and formation of N-aryl carbamates (path b) under ambient conditions.

Following a similar aminolysis procedure, one-pot catalytic
procedures have also been developed allowing the synthesis of
carbamates using in situ prepared cyclic or polycarbonate
reagents. Simple variation of the reaction conditions favourable
for epoxide/CO2 coupling gave rise to either oligomeric carbonate
or cyclic carbonate intermediates. Subsequent in situ aminolysis
of these intermediates resulted in the selective formation of either
trans- or cis-configured hydroxy carbamates (Scheme 3).[20a] The
stereodivergent synthesis leading to these carbamates was
supported by various control experiments, and conceptually this
approach offers a new tool for the stereodivergent synthesis of
CO2-derived fine chemicals albeit with moderately high yields and
sometimes relatively long reaction times (66 h) were required. At
a later stage, aminolysis of in situ prepared six-membered
carbonates obtained from oxetanes and CO2 demonstrated that
this chemistry is of use for the preparation of drug-relevant
molecules such as the muscle relaxant Carisoprodol. [20b] The Lu
laboratory reported a similar concept for chiral carbamate
synthesis from meso-epoxides using an enantiopure dinuclear
Co(III) catalyst.[21]

MINIREVIEW
carbonate intermediate was followed by dehydration resulting in
cyclic carbamate products (Scheme 5, path a). [23a] With the
introduction of secondary amine nucleophiles, the process gave
selectively rise to linear, -oxo-propylcarbamates (Scheme 5,
path b).[23b] Thus, by a judicious choice of the amine nucleophile
the chemo-selectivity towards either cyclic or linear carbamates
could be controlled. In the next section, transition metal mediated
regio-, stereo- and enantioselective transformations of
functionalized cyclic carbonates will be discussed.

3. Transition Metal-Catalyzed Decarboxylative
Transformations of Cyclic Carbonates
Scheme 3. Exemplary selective formation of cis- and trans-configured
carbamates by trapping of in situ formed oligocarbonates or cyclic carbonates
with amines. [Al] stands for an Al(III) aminotriphenolate complex, Nu is
nucleophile, Y is typically NBu4.

Cyclic carbonates also can be used as effective acylation
reagents for amines toward the preparation of five-membered
cyclic carbamates, also known as oxazolidinones. [22] Ionic liquids
(ILs) are the most frequently used catalysts for these
transformations. For example, the Gao group reported that 1butyl-3-methyl-imidazolium acetate (BmimOAc) acts as an
efficient catalyst for the acylation of anilines using ethylene
carbonate.[22a] Mass analysis suggested a cooperative activation
mode based on hydrogen bonding interaction between the ILs
and the reaction partners (Scheme 4).

Decarboxylative transformations of cyclic carbonates date
back to 1963, when Braun reported the lithium chloride catalyzed
pyrolysis of divinylethylene carbonate producing the
corresponding epoxide.[24] Seminal work from the Yoshida group
illustrated that Pd-catalyzed decarboxylative carbonylation of
cyclic carbonates toward the formation of vinyl lactones can be
readily achieved, and this represents the first transition metal
catalyzed decarboxylative transformations of VCCs (Scheme
6).[25] In the last decade, the synthetic potential of these vinyl
cyclic carbonates (VCCs) has been tremendously boosted
through the development of a wide variety of decarboxylative
functionalization processes. In sharp contrast, the catalytic
transformations of alkynyl cyclic carbonates have been much less
investigated and some notable examples will be discussed briefly.

Scheme 6. Pd-catalyzed decarboxylative carbonylation of a VCC.

Scheme 4. Acylation of amines with cyclic carbonates, and the proposed mode
of activation by the ionic liquid.

Scheme 5. Carbamate synthesis from -alkylidene cyclic carbonates.

He and co-workers described a Ag-catalyzed one-pot threecomponent strategy for carbamate synthesis starting from
propargylic alcohols, amines and CO2.[23] In the presence of
primary amines, the aminolysis of alkylidene-based cyclic

3.1. Reactions of VCCs with Nucleophiles
The transition metal catalyzed conversions of VCCs in the
presence of nucleophiles were reported in the 1990s.[26] The
reactivity of VCCs and the related vinyl epoxides proved to be
quite different.[26a,b] Moreover, substituted VCCs are much more
accessible and modular synthesis of these carbonate precursors
is generally facile using -hydroxyketones as a starting point. The
Pd- and Cu-catalyzed decarboxylative coupling of external
nucleophiles and VCCs was examined by Kleij et al. who reported
the stereoselective synthesis of a range of allylic compounds
through CN, CO, CS, CC and CB bond formation
reactions.[27] As shown in Scheme 7, in the presence of a suitable
palladium/copper precursor and ligand, the formation of a sixmembered palladacyclic or Cu-Bpin(VCC) intermediate sets up
the subsequent nucleophilic attack to afford the substituted (Z)- or
(E)-configured allylic derivatives. In the case of aryl amine
nucleophiles, extensive DFT calculations suggested that the
pathway leading to the (E)-configured allylic amines proceeds
through an epoxide intermediate requiring significantly higher
energy for the CO2 extrusion step, and thus is disfavoured under
ambient conditions.[27a] This approach based on the use of VCC
substrates as allylic surrogates offers a general entry for the
synthesis of otherwise challenging tri/tetra substituted (Z)-allylic

MINIREVIEW
scaffolds. The use of aliphatic amines in this system, however,
predominantly gave carbamate products as discussed in section
2.[27e]
The use of water as a nucleophile also proved to be feasible
leading to (Z)-1,4-but-2-ene diol formation.[27b] The application of
more challenging thiol nucleophiles required higher reaction
temperatures resulting in stereoselective allylic thioether
formation.[27c] Under suitable oxidative conditions, one-pot
synthesis of pharmaceutically relevant sulfones was achieved.[27c]
Shortly hereafter, Fernández and co-workers reported a selective
SN2´ borylation of VCCs under copper catalysis.[27d] With the
introduction of a substituent on the terminal position of the vinyl
group, asymmetric decarboxylative alkylation of VCCs with
azlactone nucleophiles could be achieved; preliminary
mechanistic studies suggested that hydrogen bonding between
the in situ formed Pd-allyl complex and the azlactone substrate is
crucial to control the regioselectivity in this CC bond formation
process.[28]

rise to the corresponding linear (Z)-configured allylic aryl ethers
(cf. Scheme 7).[29b] Related work from the Zhang group illustrated
that the asymmetric synthesis of -mono-functionalized allylic
amines is also feasible, though the process is limited to the use
of potassium phthalimide as reaction partner.[29c] In contrast, the
Pd-catalyzed asymmetric conversion of 1,2-divinylethylene cyclic
carbonate in the presence of nucleophiles is more complex. It was
proposed that both kinetic resolution and desymmetrization are
involved in the overall reaction manifold. [30]

Scheme 8. Pd-catalyzed decarboxylation of VCCs affording chiral branched
allylic compounds.

Scheme 7. Pd- and Cu-catalyzed decarboxylative formation of highly
substituted (Z)- or (E)-configured allylic scaffolds from VCCs.

By judicious choice of the ligand and palladium precursor, a
dynamic kinetic asymmetric transformation of VCCs would be
feasible if the  interconversion occurs faster than
subsequent nucleophilic attack (Scheme 8).[29] Kleij and coworkers recently developed the first general method toward the
synthesis of otherwise challenging sterically demanding chiral
-disubstituted allylic aryl amines using VCCs.[29a] The
presence of a phosphoramidite ligand proved to be key toward
the induction of high regio- and enantioselectivities. Despite the
high asymmetric induction of up to 97% ee, a detailed mechanistic
understanding of the modus operandi of the catalyst and
specifically how the catalyst controls the regioselective attack of
the amine nucleophile is not yet available.
This catalytic system tolerates various functional groups
present in either the VCC or the aryl amine reagent. The
corresponding products are essentially chiral vicinal amino
alcohols, which are of high synthetic and biological interest. This
concept was further extended to the synthesis of allylic aryl ethers
using phenol nucleophiles. The presence of Cs2CO3 was shown
to direct the nucleophilic attack of the phenol toward the sterically
crowded internal carbon center of the allyl-Pd intermediate due to
a strong interaction between oxygen and metal cationic species.
Changing the reaction conditions and the ligand gave selectively

Ir-catalyzed decarboxylative transformations were pioneered
by Krische et al. who reported on enantioselective
(hydroxylmethyl)allylation of alcohols and aldehydes.[31] The
formal carbonyl (hydroxylmethyl)allylations using alcohols involve
a transfer hydrogenation step mediated by the Ir-catalyst
providing a carbonyl nucleophile. The latter combines with the
VCC giving rise to CC bond formation between the -carbon of
the alcohol and the internal carbon center of the Ir-allyl
intermediate affording anti-1,3-diols with high enantiomeric
excess of up to 99%.[31] In contrast to these results, Zhang and
co-workers developed a protocol allowing to construct chiral 1,2diols and related ethers by directing the attack of the oxygen
nucleophile using an organoboron compound as co-catalyst. The
boron species first forms a boronate with the decarboxylated VCC
after which it interacts with the alcohol reagent or water to deliver
the branched allylic ether or 1,2-diol product. In this way,
enantioselective construction of tertiary CO bond could be
accomplished (Scheme 8; NuH = alcohols or H2O).[32]

Scheme 9. Pd-catalyzed domino process toward the synthesis of allylic
alcohols with highly functionalized quaternary carbon centers.

MINIREVIEW
Apart from externally added nucleophiles, a recent
contribution showed that the VCC itself can produce a
nucleophilic species in situ and engage with a second
decarboxylated VCC to form unusual cross-coupled products.
This formal domino process affords rather complex allylic alcohol
scaffolds with highly functionalized quaternary (racemic) carbon
centers featuring a rare combination of vinyl, aryl and aldehyde
groups (Scheme 9),[33] and developing an asymmetric version of
this cross-coupling process should be highly attractive. This
redox-neutral, stereocontrolled transformation proceeds typically
under ambient conditions and provides remarkably high yields (up
to 91%) of these polyfunctional compounds using a range of
VCCs. DFT calculations and microkinetic analysis suggest that
the final product originates from the reaction between a sixmembered palladacycle t1 and an aldehyde pro-nucleophile
derived from t1 (Scheme 9). Further experiments and calculations
revealed that there exists a subtle electronic control in the VCC
as to modify the nature of the major product of the reaction. This
work may pave the way for cross-coupling reactions based on
other similar type of vinyl-substituted heterocycles thereby
expanding the pool of synthetic complexity.
3.2. Reactions of VCCs with Electrophiles
Decarboxylative cyclization of six-membered VCCs and
isocyanate electrophiles was first reported by Tamaru et al. in
1994 to furnish stereoselectively cyclic carbamates.[34] Zhang and
co-workers later utilized this concept to develop the asymmetric
synthesis of various useful five-membered heterocycles from fivemembered VCCs and different electrophiles as reaction partners
(Scheme 10; path a);[35] the same group also reviewed these
activities.[36] In order to avoid unnecessary duplication, a detailed
discussion of this concept is not included in the present
minireview.

path b).[37a] The asymmetric version was also successfully
developed with appreciable to high enantioselectivity (80-92% ee)
and good isolated yields of typically >80%.[37b] Interestingly, the
product of the annulation process highly depended on the
substitution in the VCC substrate (R1 in Scheme 10). When R1
was an aryl group, [5+4] annulation took place and ninemembered benzofuran-fused heterocycles were selectively
formed. The use of nonsubstituted VCCs (R1 = H) afforded fivemembered spiroheterocycles via a diastereoselective formal
[3+2] cycloaddition (Scheme 10).[37a]
In addition to these aforementioned annulations, Glorius and
co-workers developed the first VCC-based enantioselective [5+2]
cycloaddition using a dual catalyst derived from a chiral NHC and
a Pd-allyl species derived from the VCC (Scheme 10, path b). [38]
The presence of a bidentate phosphine ligand was crucial to
prevent binding of the NHC to the active palladium catalyst. The
enantioselective synthesis of seven-membered structures and
beyond is quite challenging due to unfavorable entropy effects
and transannular interactions. Thus, these annulation reactions
reported by Zhao[37] and Glorius[38] pave the way for the
asymmetric synthesis of challenging larger-ring macrocycles.[39]
3.3. Cyclization through Rearrangement using VCCs
Yamada and co-workers communicated the stereospecific
and regioselective construction of highly substituted (mostly
trans)
2-cyclopentenones
via
Lewis-acid
catalyzed
decarboxylative Nazarov cyclizations of VCCs (Scheme 11).[40]
Control experiments indicated that the geometry of the substituted
allyl in the VCC substrate has a pronounced effect on the
stereochemistry of the final cyclopentenone product, and its
substitution pattern is different from classical Nazarov type
cyclizations.

Scheme 11. Lewis acid catalyzed decarboxylative Nazarov cyclization.

Scheme 10. Pd-catalyzed decarboxylative annulation of VCCs in the presence
of various electrophiles.

The Zhao group achieved a decarboxylative formation of ninemembered heterocycles through a Pd-catalyzed [5+4] annulation
procedure using N-tosyl azadienes as electrophiles (Scheme 10;

Scheme 12. Ni-catalyzed decarboxylative six-membered VCCs toward the
formation of enantioenriched cyclopropanes.

MINIREVIEW
The Krische group has developed a strategy for the
stereospecific synthesis of cyclopropanes under nickel catalysis
using enantioenriched six-membered VCCs and boroxines or
B2(pin)2 as starting materials (Scheme 12).[41] The reaction is
proposed to start from the stereospecific oxidative addition of
Ni(COD)2 to the benzylic C−O bond of the VCC with inversion of
configuration to furnish a σ-benzylnickel(II) complex. This Ni(II)
complex undergoes a decarboxylation and transmetalation
sequence in the presence of the boron reagent. The resultant
Ni(II)-alkene complex is in equilibrium through reversible
migratory insertion providing a (cyclopropylcarbinyl)nickel(II)
intermediate. Reductive elimination from the latter, presumed to
be a single diastereoisomer, releases the cyclopropane target
and regenerates the catalyst. Despite the intrinsic reactivity of the
Ni-catalyst, the process tolerates a variety of heterocyclic
functionalities. A better understanding of the origin of the
diastereoselectivity would, however, be desired.

synthesis of various allylic alcohol scaffolds (Scheme 13;
products 2-4).[44] Recent focus has shifted toward the use of more
sustainable, earth-abundant transition metal catalysts based on
cobalt and manganese. Seminal contributions from both
Ackermann and Glorius focused on the Mn(I)-catalyzed CH
allylation of indoles using either a pyridyl or N-pyrimidyl as
directing group (Scheme 13; product 4).[45] The products were
typically isolated with moderately high E/Z ratios of around 80:20.
Notably, the Yu group demonstrated that the Co-catalyzed CH
allylation of indoles can also be achieved under solvent-free
conditions using mechanochemical activation. The high-speed
ball-milling process could remarkably shorten the reaction time to
only 30 min without external heating.[46]

3.4. Allylation through CH Activation with VCCs
CH functionalization has become an important strategy
toward the build-up of more complex architectures,[42] and often a
directing group is installed in the starting material. Wang and coworkers reported in 2014 a Rh-catalyzed C−H allylation of
benzamides using VCCs. In this protocol, the alkene group of the
VCC inserts into an initially formed aryl-Rh complex. After this
insertion step decarboxylation occurs and stabilization of the
resultant Rh complex is facilitated through a bidentate
coordination of the inserted homoallyl-oxo fragment via
Rh(alkene) and Rh(O) coordination. Base-induced elimination of
the (E)-configured allylated arene regenerates the Rh catalyst.
Apart from aromatic CH activation, olefinic CH activation was
also feasible with this catalyst system (Scheme 13; product 1).[43]

Scheme 14. Co-catalyzed decarboxylative domino allylations of imidates.

More recently, the Ackermann group reported a domino
CH/NH allylation of aryl imidates by a versatile cobalt(III)
catalyst (Scheme 14).[47] This process features the formation of
substituted dihydroisoquinolines with only CO2 and H2O as byproducts. The imidate directing group is integrated into the final
product and as such, there is no need for its removal postsynthetically adding further to the atom efficiency of this Cocatalyzed transformation. This system tolerates the presence of a
relatively wide series of functional groups in the imidate substrate
including ester and amide substituents. Mechanistic
investigations (kinetic isotope effects and competition
experiments) suggest that the reaction starts with a ratedetermining CH activation step with the formation of a cationic
Co(III) complex.

Scheme 13. Transition metal catalyzed decarboxylative allylation through CH
functionalization.

This type of chemistry was further developed by other groups
using different types of directing groups (DGs) towards the

3.5. Transformations of Cyclic Alkenyl Carbonates
In addition to VCCs, alkylidene carbonates have also shown
to be useful as synthetic precursors. The oxidative addition of low
valent palladium to cyclic alkenyl carbonates results in effective
decarboxylation and generates an oxo-allyl-Pd intermediate

MINIREVIEW
(Scheme 15).[48] The zwitterionic3-allyl-Pd species is believed to
be in dynamic equilibrium with a 2-palladacyclobutanone and
incorporates both nucleophilic and electrophilic character
(Scheme 15). A range of electrophiles and reagents could trap
this reactive palladium intermediate resulting in the formation of
useful compounds such as functionalized norbornenes,
oxazolidinones, highly functionalized 2,5-dihydrofurans and silyl
enol ethers.[48a] Further application of this concept was
established by Hayashi et al. who used six-membered 2alkylidene-trimethylene carbonates as starting materials to furnish
cyclopropanated oxazolidinone products.[48b]
Cyclic alkenyl carbonates, being synthetic equivalents to
enolates upon decarboxylation, were also applied by Kakiuchi
and co-workers in the Rh-catalyzed CH functionalization of
arenes in the formation of -aryl ketones. In situ treatment of the
reaction mixture with acetic acid resulted in the generation of
valuable isocoumarins (Scheme 16).[49] The CC bond formation
was proposed to take place through migratory insertion.

Scheme 15. Pd-catalyzed decarboxylative transformations of alkylidene
carbonates. E stands for electrophile.

Scheme 17. Ni-catalyzed coupling of cyclic alkenyl carbonates and alkynes with
full atom incorporation into the final -keto-carboxylic acids.

3.6. Conversion of Alkynyl Substituted Cyclic Carbonates
Opposed to VCCs, literature on transition metal mediated
conversion of their alkynyl congeners is much more limited
despite the synthetic attractiveness of these synthons. The
reactivity of alkynyl cyclic carbonates was first explored in 1994
when Dixneuf and co-workers developed a Pd-catalyzed
formation of alkynyl -allenols from alkynyl cyclic carbonates and
terminal alkynes.[51] Following a similar strategy, the use of these
substrates was further explored by the same group in the one-pot
formation of 2,5-dihydrofurans in the presence of terminal alkenes
as reaction partners (Scheme 18).[52] It was proposed that the
reaction starts with a decarboxylation step followed by a Heck
coupling and intramolecular nucleophilic addition cyclization
resulting in the corresponding dihydrofuran products. Krause and
co-workers later reported an efficient methodology toward the
synthesis of -hydroxyallenes based on Cu-catalyzed
transformations of alkynyl cyclic carbonates proving the synthetic
potential of alkynyl cyclic carbonates.[53]

Scheme 16. C-H functionalization of arenes to afford isocoumarins.

Kimura and co-workers recently reported Ni-catalyzed
coupling reactions between cyclic alkenyl carbonates and internal
alkynes. The main difference compared to the decarboxylative
conversion of VCCs is that all atoms of the carbonate substrate
are retained in the final product (Scheme 17), i.e. this is not a
decarboxylative transformation. The presence of Me2Al(OMe) is
crucial toward the selective formation of -keto-carboxylic acids,
and other organometallic reagents such as Me3B and Me2Zn
proved to be less efficient. An eight-membered nickelacycle was
proposed to be the key intermediate in this process. [50]

Scheme 18. Pd-catalyzed decarboxylative coupling between alkynyl
carbonates and terminal alkenes to give substituted 2,5-dihydrofurans.

More recently, Zhang et al. reported on Cu-mediated
decarboxylative transformations of alkynyl carbonates into chiral
β-aminoalcohols in the presence of amine nucleophiles. [54a] Likely
the reaction manifold proceeds through a similar and well-known
Cu-allenylidene intermediate as in the case of alkynyl
epoxides.[54b] Alkynyl cyclic carbonates were also reported as
substrates in non-decarboxylative cooperative Brønsted

MINIREVIEW
acid/Mn(I) catalyzed hydroarylations under continuous flow
conditions affording (E)-configured functionalized allylic cyclic
carbonates that are useful for late-stage diversification.[55]

4. Miscellaneous Heterocyclic Substrates
4.1. Transformations of 1,4,2-Dioxazol-5-ones
1,4,2-Dioxazol-5-ones, also known as dioxazolones or cyclic
nitrile carbonates, are relatively easy to activate under mild
conditions due to a weak N‒O bond present in the heterocycle.
Since the pioneering work reported by Sauer and Mayer in
1968,[56] decarboxylative transformations based on these
heterocycles have gained much interest. These substrates have
been found especially suitable in reactions that involve C‒H
amidation of (hetero)arenes under transition metal catalysis
(Scheme 19).[57-59] The nature of the ligand is crucial for achieving
efficient turnover. For instance, the use of strong -donor ligands
such as pentamethylcyclopentadienyl (Cp*) or p-cymene (p-cym),
enabled the effective functionalization of the ortho C‒H bond of
the starting arenes. The amidation process was proposed to
proceed through a highly reactive MV-imido species followed by
reductive elimination (Scheme 19).[57a] In this regard, different
metal catalysts (Co, Ir, Rh, Ru and Cu) have been scrutinized for
the C‒H amidation of a variety of (hetero)arenes with pre-installed
directing groups.[58,59]

Scheme 19. Transition metal catalyzed C-H amidation of (hetero)arenes.

bicyclic compounds (Scheme 20). Thus, the synthesis of
quinazolines[60] and their N-oxides[61], benzimidazoles[62],
azolopyrimidines[63] and thiadiazine-1-oxides[64] was achieved in a
single step. The use of an electrophilic enaminone directing group
gave rise to 4-quinolone product.[65] The amidation of more
challenging C(sp2)‒H and C(sp3)‒H bonds can be also achieved
though the scope is limited to the use of specially designed
substrates such as oxime ethers, substituted 8-methylquinolines
and thioamides.[66]
In
the
presence
of
a
Ru(TPP)CO
(TPP
=
tetraphenylporphyrin) catalyst, dioxazolones proved to be suitable
substrates for nitrene transfer reactions (Scheme 21). The active
catalytic species is generated by dissociation of CO from the Ru
pre-catalyst, a step which can be promoted by light or thermal
energy. After decarboxylation, the N-acyl based Ru intermediate
is capable of transferring the nitrene unit to thioethers and
sulfoxides,[67] olefins and alkynes.[68] In the latter case, the addition
of CuCl2 is required as a co-catalyst allowing the formation of 2oxazolines and oxazoles.

Scheme 21. Ru-catalyzed nitrene transfer reactions using 1,4,2-dioxazol-5ones.

4.2. Cyclic Carbamate based Heterocycles
As analogues of cyclic carbonates, cyclic carbamates not only
play a pivotal role in drug discovery, agro- and medicinal
chemistry,[69] but they have also emerged as powerful building
blocks for the preparation of functionalized nitrogen-containing
heterocycles through transition-metal catalyzed decarboxylative
transformations.[70] In this regard, Lu and co-workers recently
reviewed in detail the transition metal catalyzed decarboxylative
transformation of vinyl and ethynyl benzoxazinones. [71]
Supplementary examples presented in Harrity´s review[72] further
showcase the great synthetic application potential of these
heterocycles.

Scheme 20. C‒H amidation toward the synthesis of bicyclic compounds.

With the introduction of a directing group possessing
nucleophilic or electrophilic character, subsequent intramolecular
cyclization after initial C‒H amidation is feasible giving rise to

Based on the prior achievements made in this area,[71,72] new
opportunities upon using cyclic carbamates as substrates have
been discovered. For example, Glorius and co-workers
discovered a regioselective aromatizing cascade strategy to
introduce the (2-indolyl)-methyl motif onto heteroarenes through
Mn(I)-catalyzed
C‒H
activation
employing
ethynyl
benzoxazinones (Scheme 22).[73] The key to the success of this
transformation is the use of a heteroaromatic substrate
incorporating a 2-pyridyl chelating group. This substrate is able to
promote the formation of a crucial organomanganese complex
activating the desired C(sp2)‒H bond rather than forming a Mn-

MINIREVIEW
allenylidene complex. The manganacycle further reacts with the
benzoxazinones through an aromatizing cascade cyclization
releasing the diheteroarylmethane product (Scheme 22).
Preliminary mechanistic experiments suggested that the C‒H
bond cleavage is probably not the rate-limiting step, but rather
olefin coordination and subsequent insertion. The order of the
cyclization and protonation steps remained unclear and may
occur as presented in scheme 22 or vice versa.

Acknowledgements
We thank the CERCA Program/Generalitat de Catalunya, ICREA,
the Spanish MINECO (CTQ2017-88920-P, SEV-2013-0319, and
FPI fellowship to J.E.G.) and AGAUR (2017-SGR-232). J.X
thanks the CSC (2016-06200061) for a predoctoral fellowship.
W.G thanks the starting funding scheme of Xi’an Jiaotong
University.

Conflict of Interest
The authors declare no conflict of interest.
Wusheng Guo earned his PhD degree
in Chemistry in 2014 from the UAB
under the supervision of Prof. Roser
Pleixats and Dr. Alexandr Shafir. Then
he joined ICIQ in Tarragona (Kleij
group) as a postdoc. In 2018, he was
appointed full professor in Frontier
Institute of Science and Technology
(FIST) of Xi’an Jiaotong University
(China). His research interests include hypervalent iodine
chemistry, nanoparticles and transition metal catalysis.
Scheme 22. Mn(I)-catalyzed C‒H (2-indolyl)methylation using propargylic
benzoxazinones.

5. Conclusion and Outlook
This minireview undoubtedly demonstrates the synthetic
renaissance of heterocycles known as cyclic organic carbonates.
In the last decade, a number of new catalytic transformations
have displayed exciting new, improved or amplified reactivity and
selectivity features. One of the main advantages of these
heterocyclic scaffolds is their ease of synthesis and their modular
character making them ideally suited for synthetic applications
and explorations. Transition metal chemistry concepts can be
merged with the use of VCCs and related heterocycles to provide
new opportunities such as those described in this minireview.
These include C‒H bond functionalization, stereo- and
enantioselective Tsuji-Trost allylic alkylations, and unexplored
potential for natural product synthesis.
While most of the synthetic conversions are still based on
expensive transition metal catalysts, new potential for VCC
valorization requires the development of cheaper catalytic
strategies based on abundant metal alternatives. Furthermore,
the development of efficient domino processes or cooperative
catalytic systems that utilize these VCC substrates would
certainly be attractive,[74] though the combination of different
catalysts and/or sequential synthetic steps represents a
significant challenge. A practical operational window needs to be
established for all steps/catalysts matching the requirements of
each transformation without affecting the overall catalytic
performance. Despite the intrinsic complexity, such multi-step
designer preparations can be an attractive future direction for
VCC transformations while contemplating a growing importance
of decarboxylative functionalization in synthetic chemistry.

José Enrique Gómez received his BSc
and MSc degrees from the University of
Valladolid
(Spain)
under
the
supervision of Prof. Alfonso PérezEncabo. Since 2015, he has been a
PhD student at ICIQ. He is currently
working on transition metal catalyzed
stereocontrolled transformations.
Àlex Cristòfol obtained his BSc and
MSc (2017) degrees in chemistry from
the URV in Tarragona. He is currently
pursuing doctoral studies at the ICIQ in
the group of Prof. Arjan W. Kleij. His
research interests include metal
catalysis, and synthesis of biologically
active compounds.
Jianing Xie received his MSc degree
from Nankai University in 2016 under
the supervision of Prof. Liang-Nian He.
Currently he is a PhD student in the
research group of Prof. Arjan W. Kleij at
ICIQ. His current research focus is on
stereo/enantioselective transition-metal
catalyzed C–N/C–O bond formations.
Arjan W. Kleij obtained his PhD from
the University of Utrecht in 2000. After
postdoctoral appointments in Madrid
(UAM) and Amsterdam (UvA), he
started his independent career at ICIQ
in 2006, and was promoted to ICREA
Professor in 2011. His research
interests include small molecule
activation
and
new
biopolymer
development.

MINIREVIEW
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MINIREVIEW
Entry for the Table of Contents:

MINIREVIEW
How to transform a ring: Functionalized
cyclic carbonates and related heterocycles
find increasing synthetic utility using
predominantly transition metal catalysis. In
particular, vinyl- and alkynyl-substituted
substrates have been at the forefront of
these developments with decarboxylative
approaches being prevalent. An overview
of recent developments towards new
regio- and stereoselective transformations
useful in fine chemical and pharmarelevant synthesis are presented.

Wusheng Guo,* José Enrique Gómez,
Àlex Cristòfol, Jianing Xie, and Arjan W.
Kleij*

Page No. – Page No.

Catalytic Transformations of
Functionalized Cyclic Organic
Carbonates