Copper(II)-catalysed oxidative carbonylation of aminols and amines in water: A direct access to oxazolidinones, ureas and carbamates

Article abstract of DOI:10.1016/j.molcata.2015.06.007

Copper(II) chloride catalyses the oxidative carbonylation of aminols, amine and alcohols to give 2-oxazolidinones, ureas and carbamates. Reaction proceeds smoothly in water under homogeneous conditions (P_tot = 4 MPa; P_O2 = 0.6 MPa, P_CO), at 100°C in relatively short reaction times (4 h) and without using bases or any other additives. This methodology represents an economic and environmentally benign non-phosgene alternative for the preparation of these three important N-containing carbonyl compounds.

Full text of DOI:10.1016/j.molcata.2015.06.007

Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
Contents lists available at ScienceDirect
Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Copper(II)-catalysed oxidative carbonylation of aminols and amines
in water: A direct access to oxazolidinones, ureas and carbamates
Michele Casielloa, Francesco Iannonea, Pietro Cotugnoa,∗, Antonio Monopolia,
Nicola Cioffia, Francesco Ciminalea, Anna M. Trzeciakc, Angelo Naccia,b,∗
a Department of Chemistry, University of Bari “Aldo Moro”, Via Orabona, 4, 70126 Bari, Italy
b CNR – ICCOM, Department of Chemistry, University of Bari “Aldo Moro”, Via Orabona, 4, 70126 Bari – Italy
c University of Wrocław, Faculty of Chemistry, 14 F. Joliot-Curie, 50-383 Wrocław, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 6 April 2015
Received in revised form 4 June 2015
Accepted 5 June 2015
Available online 18 June 2015
Copper(II) chloride catalyses the oxidative carbonylation of aminols, amine and alcohols to give 2-
oxazolidinones, ureas and carbamates. Reaction proceeds smoothly in water under homogeneous
conditions (Ptot = 4 MPa; PO2 = 0.6 MPa, PCO), at 100 ◦C in relatively short reaction times (4 h) and with-
out using bases or any other additives. This methodology represents an economic and environmentally
benign non-phosgene alternative for the preparation of these three important N-containing carbonyl
compounds.
Keywords:
© 2015 Elsevier B.V. All rights reserved.
Oxidative carbonylation
Copper halides
2-Oxazolidinones
Carbamates
Ureas
1. Introduction
safer phosgene equivalents, such as triphosgene, activated carbon-
ates (DMC and DET), carbonyl diimidazole, carbamoyl chlorides,
2-Oxazolidinones, ureas, and carbamates are useful compounds
that find application in many practical fields. 2-Oxazolidinone and
carbamates are successfully employed as intermediates in the syn-
thesis of agrochemical, pesticide, herbicide and pharmaceutical
agents [1], but also as solvents [2] and chiral auxiliaries [3]. Acy-
lation of 2-oxazolidinones is also a frequently used method for the
synthesis of valuable compounds such as amino acids [4].
Ureas are used as dyes for cellulose fibers, antioxidants in
gasoline, corrosion inhibitors, plant growth regulators, pesticides,
insecticides, and as tranquilizing and anticonvulsant agents [5].
Many urea derivatives have displayed a wide spectrum of biological
activity [6]; in particular, as inhibitor of HIV protease enzyme [7].
In addition, they are advantageous intermediates in the production
of carbamates [8].
chloroformates, CO and CO2 as the source of the carbonyl moiety
[4,10].
Particularly, for the synthesis of cyclic carbamates, reaction of
aziridines, aminoalcohols, primary or acetylenic amines with CO2
have been investigated [11]. However, most of these compounds
are still usually prepared from phosgene as the carbonylating agent.
Particularly attractive from the standpoint of atom economy is
the oxidative carbonylation of amino compounds, a process that
has been considerably studied in the last decade. This reaction is
significantly advantageous compared with the above-mentioned
methods, since it avoids hazardous and/or expensive reagents and
requires milder temperature conditions (373–423 K). Transition
metal such as Pd [12], Ru [13], and Rh [14], have been found to
promote the oxidative carbonylation of amines and aminols. How-
ever, two issues, related to the high cost of these catalysts and the
toxicity of utilized solvents (DMF, DMA etc.), remained unsolved.
The use of cheaper and non-noble metals is currently explored
and interesting results have been obtained with cobalt catalysts
[15], which however required Schiff-base ligands and iodine or N-
containing bases as promoters. Moreover, cheap metals such as
copper, except for one example which involves a Cu(I)-complex
bearing however an expensive N-heterocyclic carbene as ligand
[16] have in fact remained unexplored. In addition, all these reac-
The classical synthesis of these compounds from the corre-
sponding amino derivatives is based on the use of toxic and/or
corrosive reagents, such as phosgene or isocyanates [9]. In recent
years, however, alternative routes have been developed that utilize
∗
Corresponding authors. Fax: +39 080 5442129.
E-mail addresses: pietro.cotugno@uniba.it (P. Cotugno), angelo.nacci@uniba.it
(A. Nacci).
http://dx.doi.org/10.1016/j.molcata.2015.06.007
1381-1169/© 2015 Elsevier B.V. All rights reserved.

M. Casiello et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
9
tions are carried out in common organic solvents as dioxane, THF,
CH3CN, DMA, DMF, which are toxic and therefore banned from the
industrial practise [17].
works also under the safety conditions even if with longer reac-
tion times. This result has been added in Table 1 (entry 16) and the
procedure described in Section 2.3.
As described in our previous work, we have found that oxidative
carbonylation of diols [18] and glycerol [19] can be easily promoted
by the inexpensive CuCl2 salt as catalyst without using special lig-
ands and/or promoters. Following our success on diols, we decided
to extend such an oxidative carbonylation to amines and aminoal-
cohols developing a copper-based catalytic system for the synthesis
of 2-oxazolidinone, ureas and carbamates in the absence of addi-
tives and using water as the solvent [Eqs. (1)–(3)].
2.3. Catalytic tests
Catalytic tests were carried out in a 55.6 mL stainless steel auto-
clave mounted in an electrical oven having a magnetic stirrer on
its base. Catalyst, additives, solvent and reagents were introduced
in a glass vial (∼20 mL) and placed into the autoclave, in order to
O
CuIIcat
water
(1)
HN
O
+
H2O
H2N
R
OH + CO + 1/2 O2
R
O
CuIIcat
water
(2)
(3)
+
H2O
H2O
2
R
NH2 + CO + 1/2 O2
RNH
RNH
NHR
OR1
O
CuIIcat
water
R
NH2
R1 OH + CO + 1/2 O2
+
+
avoid any contact with metal walls. Under these conditions, the free
volume for gaseous mixture is in the range 35 ÷ 40 mL.
2. Experimental
In a typical experiment the glass vial was charged with a dou-
bled distilled water solution (5.0 mL) of substrate (amine or aminol)
(4 mmol), catalyst (CuCl2, 0.40 mmol), which appeared transparent
and deep blue colored. The vial was introduced into the autoclave
which was sealed, purged and charged with O2 (0.6 MPa) and CO up
to a total pressure of 4 MPa. Under these conditions, the substrate
should be deemed the limiting reagent, also taking into account the
head space of the autoclave and the stoichiometry of the carbony-
lation process [Eq. (1)].
2.1. Materials and general procedure
Copper salts [CuCl2, CuBr2] were dried under vacuum overnight
before their use. PdCl2, aminols, amines, alcohols, diphenylphos-
phine, 2-vinylpyridine, solvents (CH3CN, N,N-dimethylformamide
DMF, N,N-dimethylacetamide DMA, CH3OH), ligands (pyri-
dine, triphenylphosphineoxide 2,2ꢀ-bipyridyl), external standard
(butanone), and Na2CO3 were Aldrich or Fluka products and were
used as received.
The mixture was heated at 100 ◦C and allowed to react for 4 h.
After this time, the autoclave was cooled at room temperature and
then the residual gas was evacuated.
Identification of reaction products was performed via GC–MS by
comparison of their MS spectra with those reported in the litera-
ture (and with the help of NIST database). A complete list of mass
spectral data of the major reaction products, including by-products,
was reported into the supplementary material section. Quantitative
analysis of reaction mixture was accomplished by GC–MS using
butanone as an external standard. Conversions and yields were
reported in Tables 1–3.
Comparative experiment carried out under the safety condi-
tions (CO:O2 = 15:1 molar ratio), was performed on a H2O solution
(5.0 mL) of aminol (2,6 mmol), catalyst (CuCl2, 0.26 mmol). The vial
was introduced into the autoclave which was sealed, purged and
charged with O2 (0.25 MPa) and CO up to a total pressure of 4 MPa.
Under these conditions, the mixture was heated at 100 ◦C and
allowed to react for 8 h. After this time, the reaction mixture was
analysed by GC–MS for assessing conversions and selectivities as
reported in Table 1, entry 18.
Copper
complex
(29H,
31H-phthalocyaninato(2-)-
N29,N30,N31,N32) copper(II) (II) (INTATRADE GmbH) was
commercially available, dichloro(2,2ꢀ-bipyridyl) copper(II) (III)
[20], dichlorobis(triphenylphosphineoxide) copper(II) (I) [21], and
dichloro[2-(␤-diphenylphosphinoethyl)
pyridine]palladium(II)
(IV) [22] were prepared according to the literature.
Reactions products were detected by GC–MS and identified
by comparison of their IR and MS spectra with literature data
(see supplementary material). FT-IR spectra were recorded on a
Perkin–Elmer Spectrum BX spectrophotometer. GC–MS analyses
were carried out with an Agilent GC 6850 (equipped with a capil-
lary column: HP-5 MS, 30 m) linked to an Agilent 5975C selective
mass detector.
Special care was devoted to the cleaning of the equipment (glass
vials, magnetic stirrer, etc.) carried out with aqua-regia to prevent
metal contaminations.
2.2. Safety advices
It is well known that the high-pressure experiments with CO/O2
mixtures are potentially explosive in the range 16.7–93.5% [23] and
may represent a significant risk. Consequently, experiments with
compressed gases should only be carried out in conjunction with
the use of suitable equipments and special care. In this work, auto-
claves equipped with appropriate rupture discs (strength 10 MPa)
and mixtures of CO/O2 = 6:1 ca. molar ratio (∼85%) very close to the
upper limit of the above-mentioned range were used. In any case,
a comparative carbonylation experiment has been performed at a
CO:O2 = 15:1 molar ratio (93.7%), demonstrating that the catalyst
3. Results and discussion
3.1. Optimization of catalysis conditions
In our previous works [18,19] we had shown that the presence
of water, even in small quantities, negatively influenced the cat-
alytic activity of copper(II) in the oxidative carbonylation of polyols.
This damaging effect was ascribed to a competitive carbonylation

10
M. Casiello et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
Table 1
Optimisation of reaction conditions.a
O
OH
cat. CuII
O
HN
+
H2O
H2N
T °C, CO/O2 (4 MPa), 4 h
CH3
solvent
1
CH3
Entry
Catalyst
Solvent
Additive
T (◦C)
Conv.b (%)
Sel.%b (%)
1
2
3
4
5
6
7
8
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuCl2
CuBr2
CH3CN
DMF
H2O
CH3CN
CH3CN
DMF
CH3OH
THF
H2O
H2O
H2O
H2O
Py
Py
Py
Na2CO3
100
100
100
100
100
100
100
100
100
80
140
100
100
100
100
100
22
20
25
95
90
45
55
50
55
65
45
46
50
90
70
55
30
10
20
40
90
–
–
–
–
–
–
–
–
–
–
–
–
100
100
95
76
50
76
15
20
25
27
70
9
10
11
12
13
14
15
16c
(Ph3PO)2CuCl2 (I)
(Phthalocyanine)Cu(II) (II)
(Bipy)CuCl2 (III)
CuCl2
H2O
H2O
H2O
H2O
a
General reaction conditions: 1-amino-2-propanol (4 mmol), CuII cat. (10 mol%), additive (0.5 equiv. respect to Cu) in 5 mL of solvent, heated for 4 h under stirring under
a gaseous mixture of O2 (0.6 MPa) and CO (3.4 MPa).
b
Evaluated via GC–MS. Selectivities are referred to the moles of cyclic carbamate formed (see Section 2).
Reaction carried out under safety conditions for 8 h (CO:O2 = 15:1 molar ratio, see Sections 2.2 and 2.3).
c
of water promoted by Cu(II) which consumes CO and produces
CO2. This process became dominant at high conversion values of
the starting diol, when concentration of water, by-product of the
carbonylation, reaches high values into the reaction medium.
Extending these investigations to amino compounds, we found
that this competition is greatly reduced, presumably because of the
strong affinity of the amino group toward Cu2+, and this observation
encouraged us to explore the use of water as eco-friendly solvent
for the carbonylation of aminols and amines.
Preliminary experiments were focused on ␤-aminols for the
synthesis of 2-oxazolidinones. With these substrates we found that
copper(II) catalysts promote the oxidative carbonylation into their
cyclic carbamates according to the stoichiometry of Eq. (4) and that
catalytic efficiency is affected by reaction times and temperature
absence of bases or other additives (Table 1, entries 4–8). How-
ever, under these ligand-free conditions, the use of organic solvents
such as CH3CN, DMF, THF and CH3OH gave poor selectivities, below
65% (Table 1 entries 5–8). Surprisingly, the use of water produced
only a slight decrease of conversions but lowered significantly the
formation of by-products (Table 1, entry 9).
Reaction time showed a narrow influence, with conversions that
reached a plateau after 8 h, while temperature affected carbony-
lation in a predictable manner: at lower temperatures (80 ◦C) a
decrease in conversions was found, while an increase of tempera-
ture at 140 ◦C had no effect on conversion but produced a dropping
of selectivity (Table 1, entries 10–11).
Final optimization tests were focused on searching for other
copper catalyst sources. As shown in Table 1 (entries 12–15), cop-
conditions.
O
OH
CuIIcat
O
HN
+
CO + 1/2 O2
H2N
+
H2O
(4)
R
R
The optimisation of the reaction conditions was surveyed on the
model substrate 1-amino-2-propanol (Table 1), using a procedure
similar to that employed in the previous protocol for diols [18]:
4 mmol of aminol, 0.4 mmol of Cu(II) catalyst (10 mol%), 0.2 mmol
of pyridine as ligand dissolved in 5 mL of solvent, heated for 4 h
under a CO/O2 mixture (4 MPa, 6:1 ca. molar ratio). Preliminary
blank reaction showed a total catalysis inhibition in the absence of
copper, thus confirming that this metal is necessary to promote the
process.
As can be seen from data in the Table 1, the beneficial effect
of pyridine, which was crucial in the case of glycerol [19], totally
disappeared with this aminol (Table 1, entries 1–3). This suggests
that the presence of pyridine should afford the saturation of the
metal center, which is chelated by the aminol substrate, leading to
a remarkable inhibition of the catalytic process (see Section 3.3).
This hypothesis is supported by the good conversion values
observed by replacing pyridine with Na2CO3 or working in the
per salt CuBr2 and Cu(II) complexes I-III furnished disappointing
results, also in the case of dichlorobis(diphosphineoxide) copper(II)
catalyst (I), that had displayed good activity with glycerol [19].
3.2. Substrate scope: synthesis of 2-oxazolidinone, carbamates
and ureas
With the optimised conditions in hand, we extended oxidative
carbonylation to several nucleophilic substrates such ␤-aminols,
diamines, amines and alcohols. Data reported in Table 2 show that
CuCl2, under relatively mild conditions in water, exerted a good
catalytic activity toward a series of ␤-aminols, providing the cor-
responding 2-oxazolidinones in moderate to good yields.
As already reported [16], aromatic aminols showed a different
behavior. Indeed, in place of the carbonylation process, they expe-
rienced an oxidative condensation reaction promoted by copper.

M. Casiello et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
11
Table 2
Synthesis of 2-oxazolidinones.a
O
CuCl2 cat.
OH
H2N
HN
R1
O
water, 100 °C
CO/O2 (4 MPa)
R1
R2
R2
Run
Substrate
Product
Conv.b (%)
Sel.%b (%)
O
H2N
OH
O
1
2
3
HN
76
90
94
91
1
O
H2N
H2N
OH
OH
76
O
HN
HN
2
O
O
O
75
3
H2N
OH
O
HN
O
4
72
94
4
H2N
OH
OH
O
5
HN
75
92
5
O
CH3NH
CH3
6
73
92
O
N
6
O
N
O
NH2
OH
7
61
60
NH2
7
a
General reaction conditions: substrate (4 mmol), CuII cat. (10 mol%), 5 mL of solvent, heated under stirring under a gaseous mixture of O2 (0.6 MPa) and CO (3.4 MPa).
Evaluated via GC–MS. Selectivities are referred to the moles of 2-oxazolidinones formed (see Section 2).
b

12
M. Casiello et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
Table 3
Synthesis of ureas and carbamates.a
O
cat. CuCl2
R NH2
+ R NH2
RNH C XR
water, 100 °C, 4 h
(or R-OH)
(X= NH or O)
CO/O2 (4 MPa)
Entry
Substrates
R-NH2
Products
Conv.b (%)
Sel.%b (%)
R-OH
O
1
2
PrNH2
–
90
97
66
92
PrNH C NHPr 8
O
MeOH
PrNH C OMe 9
O
3
4
5
BuNH2
–
89
96
96
65
91
62
BuNH C NHBu 10
O
MeOH
BuNH C OMe 11
O
EtOH
BuNH C OEt 12
O
6
7
Et2NH
–
75
85
51
90
Et2N C NEt2 13
O
MeOH
Et2N C OMe 14
O
8
9
CyNH2
–
91
96
49
95
CyNH
C
O
NHCy 15
MeOH
–
CyNH C OMe 16
O
n-
12H23NH2
10
11
80
81
60
70
n-C12H25NH C NHC12H25-n
C
O
MeOH
n-C12H25NH
C
OMe 18
NH
O
OH
H2N
19
12
13
14
90
85
51
O
NH
O
H2N
OH
NH2
<5%c
20
21
O
NH
H2N
H2N
O
<5%
–
NH
15
<5%
80
–
90
NH
O
16d
NH2
22
NH
General reaction conditions: substrate (4 mmol), CuII cat. (10 mol%), of doubled distilled water (5 mL), T = 100 ◦C for 4 h under O2 (0.6 MPa) and CO (3.4 MPa).
Evaluated by GC–MS.
a
b
c
Linear ␦-hydroxylated ureas are the major reaction products.
Reaction carried out with Pd(PNPy)Cl2 catalyst (IV) (1 mol%, see Fig. 3).
d

M. Casiello et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
13
O
O
O
NH
R
R
C
R
NH
R
NH
(V)
H
N
(VI)
(VII)
O
Fig. 1. Major carbonylation by-products of amines and aminols (R = alkyl or -
CH2CH2OH).
As an example, 2-aminophenol afforded 2-amino-3H-phenoxazin-
3-one (7) as main product (Table 2, run 7). Under these conditions,
1,2-disubstituted aminols proved to be less reactive.
Further investigations showed that this copper catalyst system
in water could also be successfully applied to the oxidative car-
bonylation of simple amines to produce ureas and carbamates (in
the latter case an alcohol must be present into the reaction mixture,
Table 3).
Excellent conversions (75% ÷ 96%) were observed with aliphatic
monoamines like n-propylamine, n-butylamine, diethylamine,
cyclohexylamine and n-dodecylamine (Table 3, entries 1,3,6,8,10,
respectively).
However, reactions in water on these substrates occurred with
lower selectivity (up to 65%) respect to aminols, due to the
formation of by-products arising from partial carbonylation (pre-
dominantly formamides V and isocyanates VI), or from oxidative
coupling reactions, that afforded oxalamides VII (see Fig. 1). These
by-products were also observed in the case of ␤-aminols although
in much smaller percentages (see Section 2).
The nature of alkyl chain (R) somehow affected reactivity of
these alkylamines in water. Indeed, substrates bearing longer
chain afforded slightly lower conversions, because of their lower
solubility in water (Table 3, entries 1,3,10). At the same time, cyclo-
hexylamine and diethylamine, probably due to steric reasons, gave
also a decrease of selectivity (Table 3 entries 6, 8).
In contrast, oxidative carbonylation of the same aliphatic
amines carried out in the presence of short-chain alcohols resulted
highly efficient, affording the corresponding linear carbamates in
high yields and moderate to good selectivities (Table 3, entries
2,3,5,7,9,11).
Notably, ␥- and ␦-aminols promptly reacted with CO and O2
giving good conversions but poor selectivities due to the greater
distance between the two functional groups OH- and -NH2 that
would favour the competitive intermolecular carbonylation pro-
cess and produce great amounts of linear ␥- and ␦-hydroxylated
ureas (Table 3, entries 12,13).
Fig. 2. The plausible carbonylation mechanism of ␤-aminols (S = solvent).
the process should proceed with the formation of the alkoxycar-
bonyl copper species IX [path b)], passing most probably through a
preliminary ligand exchange between CO and hydroxyl group. The
reductive elimination should afford 2-oxazolidinone product and
Cu(0) [path c)], and the latter should be re-oxidized by molecular
oxygen to the active species Cu(II) [path d)].
It should be noted that the distinctive feature of this protocol
on ␤-aminols is the high stability of copper catalyst toward the
detrimental effect of water, which has been the main trouble of
reactions with diols and glycerol [18,19], This could be explained
with the chelating effect of these substrates that would give very
stable square planar complexes X as depicted in Fig. 3 [25].
This coordination is crucial for reactivity these substrates bear-
ing two functionalities with different ligand power. Indeed, the
amino group can act as a “hook” onto the metal center, prevent-
ing the damaging effect of water, while the hydroxyl group, being a
weaker ligand, could be more promptly replaced, at the appropriate
time, by coordination of CO allowing the catalyst to work.
It can also be assumed that in the case of diamines the strong
chelating action could impedes the coordination of carbon monox-
ide CO totally inhibiting the catalysis (see Fig. 3, complex XI). This
detrimental effect is clearly observed in the case of 1,2- and 1,3-
diamines (Table 3, entries 14,15) and is similar to that observed
with glycerol in reactions carried out in the presence of strong
chelating ligands like o-phenantroline and bipyridyl [19].
To verify this assumption we carried out the oxidative carbony-
lation of ethylendiamine in the presence of a different metal center
such as palladium, for which amino groups show a lower affinity.
Specifically, reaction was performed in H2O in the presence of the
complex Pd(PNPy)Cl2 (IV) (see Fig. 3) and NaI as cocatalyst [26]. As
3.3. Mechanistic insights
Based on our previous works [18,19] and the analogous reac-
tions promoted by palladium [24], we propose the mechanism
shown in Fig. 2 for the oxidative carbonylation of a generic ␤-
aminol.
In a first instance, it can be postulated the formation of the
chelated species VIII [path a)], as evidenced by the deep blue color
assumed by the starting reaction mixture (see Section 2.3). Then,
H2
N
H2
N
H2
N
H
O
R
R
Cu2+
Cu2+
P
N
Pd
R
R
N
N
O
H
N
H2
H2
H2
Cl
Cl
(X)
(XI)
(IV)
Fig. 3. Square planar complexes of copper and palladium.

14
M. Casiello et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 8–14
expected, catalyst did work without inhibition (Table 3, entry 16),
thus confirming our hypothesis.
(b) M. Kumar, M.V. Hosur, Eur. J. Biochem. 270 (2003) 1231–1239;
(c) A.R. Katritzky b, A. Oliferenko, A. Lomaka, M. Karelson, Bioorg. Med. Chem.
Lett. 12 (2002) 3453–3457.
[8] (a) S. Salvestrini, P. Di Cerbo, S. Capasso, J. Chem. Soc. Perkin Trans. 2 (11)
(2002) 1889–1893;
4. Conclusions
(b) H.S. Kim, Y.J. Kim, H. Lee, S.D. Lee, C.S. Chin, J. Catal. 184 (1999) 526–534;
(c) S.P. Gupte, A.B. Shivarkar, R.V. Chaudari, Chem. Commun. (2001)
2620–2621;
(d) J. Yamaguchi, Y. Shusa, T. Suyama, Tetrahedron Lett. 40 (1999) 8251–8254;
(e) N.V. Kaminskaia, I.A. Guezi, N.M. Kostic, J. Chem. Soc., Dalton Trans. (1998)
3879–3886.
In summary, we have successfully developed an efficient and
simple CuCl2 based catalyst system without any additive for the
oxidative carbonylation of ␤-aminoalcohols, amines and alcohols,
to produce 2-oxazolidinones, disubstituted ureas and carbamates.
This is the second example in the literature [16] on the use of cop-
per catalyst in the oxidative carbonylation of amino alcohols and
amines, but this protocol presents the advantage of using water as
an eco-friendly solvent that improves sustainability of the process.
This methodology represents an economic and environmentally
benign non-phosgene alternative for the preparation of these three
important N-containing carbonyl compounds.
[9] (a) G. Sartori, R. Maggi, in: S.V. Ley, J.G. Knight (Eds.), Science of Synthesis, vol.
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Acknowledgment
We thank University of Bari, Ministry of University of Italy
(MIUR) and Regione Puglia (“PON Ricerca
2007–2013–Avv. 254/Ric. del 18/05/2011, Project PONa3 00369
“Laboratorio SISTEMA”) for the financial supports.
e Competitività”
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