Nickel-Catalyzed Synthesis of N-(Hetero)aryl Carbamates from Cyanate Salts and Phenols Activated with Cyanuric Chloride

Article abstract of DOI:10.1002/cctc.202000876

A simple and efficient domino reaction has been designed and employed for the one-pot synthesis of N-(hetero)aryl carbamates through the reaction between alcohols and in-situ produced (hetero)aryl isocyanates in the presence of a nickel catalyst. The phenolic C?O bond was activated via the reaction of phenol with cyanuric chloride (2,4,6-trichloro-1,3,5-triazine (TCT)) as an inexpensive and readily available reagent. This strategy provides practical access to N-(hetero)aryl carbamates in good yields with high functional groups compatibility.

Full text of DOI:10.1002/cctc.202000876

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: Nickel-Catalyzed Synthesis of N-(Hetero)aryl Carbamates from
Cyanate Salts and Phenols Activated with Cyanuric Chloride
Authors: Iman DindarlooInaloo, Mohsen Esmaeilpour, Sahar Majnooni,
and Ali Reza Oveisi
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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to this Accepted Article as a result of editing. Readers should obtain
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content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.202000876
Link to VoR: https://doi.org/10.1002/cctc.202000876
01/2020

10.1002/cctc.202000876
ChemCatChem
FULL PAPER
Nickel-Catalyzed Synthesis of N-(Hetero)aryl Carbamates from
Cyanate Salts and Phenols Activated with Cyanuric Chloride
Iman Dindarloo Inaloo,*[a] Mohsen Esmaeilpour,*[a,b] Sahar Majnooni,[c] and Ali Reza Oveisi[d]
Dedication ((optional))
Abstract: A simple and efficient domino reaction has been designed
and employed for the one-pot synthesis of N-(hetero)aryl
carbamates through the reaction between alcohols and in-situ
harsh reaction conditions, and multiple-step synthetic
procedures.[9-12] Hence, the introduction and design of new and
efficient synthetic methods for straightforward access to
carbamates are highly desirable.[2, 3]
produced (hetero)aryl isocyanates in the presence of
a nickel
catalyst. The phenolic C-O bond was activated via the reaction of
phenol with cyanuric chloride (2,4,6-trichloro-1,3,5-triazine (TCT)) as
an inexpensive and readily available reagent. This strategy provides
practical access to N-(hetero)aryl carbamates in good yields with
high functional groups compatibility.
Metal-catalyzed reactions of aryl halides with isocyanate anion
O
[M], KOCN
a)
[M]= Pd, Cu, Ni
Ar
R
Ar X
R OH
N
O
H
X= I, Br , Cl
Metal-catalyzed reactions of aryl C-O electrophiles with isocyanate anion
O
Previous works:
Ar OH
Introduction
[Pd], NaOCN
R OH
Ar
R
b)
c)
Ar OTf
N
H
O
Carbamates are the core structures of many natural and
synthetic compounds with a wide range of applications in the
agriculture, biological, and pharmaceutical industries.[1] However,
the traditional synthetic methods for the preparation of
carbamates suffer from the use of highly toxic phosgene or its
derivatives.[2, 3] Recently, the synthesis of carbamates using CO2
Ar
This work:
O
O
N
N
2) [Ni], KOCN
R OH
1) TCT
Ar
R
Ar
Ar OH
Ar
N
O
O
N
O
H
TAT
and CO as green carbonyl source alternatives for phosgene has
been attracted great attention by researchers.[4,
However,
5]
Scheme 1. Metal-catalyzed reactions for the synthesis of N-aryl carbamates
these chemical transformations are performed under severe
reaction conditions and need to follow strict safety guidelines.[4, 5]
Since the synthesis of isocyanate via reacting diethyl sulfate and
potassium cyanide by Wurtz in 1848, it has become one of the
most popular and beneficial precursors for the synthesis of
diverse organic compound specially carbamates.[6] Although the
high reactivity of isocyanates is favorable for many industrial
processes, however, their moisture-sensitive nature limits the
scope of their applications.[7] To address the issue, the in-situ
formation of isocyanates has been reported as the best
alternative approach.[8] Hofmann,[9] Curtius,[10] Lossen,[11] and
Schmidt's rearrangements have predominantly been used to
generate isocyanates in-situ during the processes.[12] However,
these reactions are limited by the availability of starting materials,
Very recently, transition-metal catalyzed reactions of the
isocyanate anion with aryl halides towards the carbamates via
in-situ formation of aryl isocyanates, as reactive intermediates,
have been successfully developed (Scheme 1, a).[13] Besides,
activated phenolic compounds as the reactive aryl C-O
electrophiles have been used as alternatives to aryl halides.[14] In
recent years, the phenol derivatives have received much
attention as prevailing and environmentally friendly alternatives
for being used instead of aryl halides.[15] In most cases, the
phenolic compounds are converted to the corresponding aryl
C-O
electrophiles
which
served
as
starting
materials/intermediates in the metal-catalyzed reactions.[16]
However, to the best of our knowledge, the literature survey
showed only one report dealing with the direct conversion of aryl
triflates reacted with isocyanate anion to carbamates in the
presence of Pd catalyst (Scheme 1, b).[17] More recently, the
in-situ activation of phenol derivatives with TCT towards the
production of aryl-triazine ethers as the C-O electrophiles has
been reported by Iranpoor et al.[18]
[a]
Dr. Iman Dindarloo Inaloo, Dr. Mohsen Esmaeilpour
Chemistry Department, College of Sciences, Shiraz University,
Shiraz 71946 84795, Iran.
E-mail: iman.dindarlooinaloo@gmail.com
Dr. Mohsen Esmaeilpour
Chemistry and Process Engineering Department, Niroo Research
Institute,Tehran 1468617151, Iran.
Dr. Sahar Majnooni
Chemistry Department, University of Isfahan, Isfahan 81746-73441,
Iran.
[b]
[c]
[d]
In a continuation of our previous work on the construction of
C–C and C–N bonds with the cleavage of C–O bonds in the
presence of nickel catalysts,[19] herein, we report the reaction of
activated phenolic compounds with TCT (2,4,6-triaryloxy-1,3,5-
triazine (TAT)) and cyanate anion which results in the in-situ
formation of phenyl isocyanate in the presence of nickel
catalysts followed by reacting the phenyl isocyanates with
alcohol, as the nucleophile, to afford N-aryl carbamates
(Scheme 1, c).
Dr. Ali Reza Oveisi
Department of Chemistry, Faculty of Sciences, University of Zabol,
Zabol 98615-538, Iran.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/cctc.202000876
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Results and Discussion
studied (Table 1, entries 8–17). As indicated in table 1, the
bidentate dppf was found to be the most effective ligand for the
catalytic reaction. We also examined the reaction in the
presence of the different loadings of catalyst (Ni(COD)2) and
ligand (dppf) (Table 1, entries 5 and 18-22). As shown in table 1,
10 mol% of Ni(COD)2 and 10 mol% of dppf were favorable for
the proceeding reaction, providing the highest product yield of
86% (entry 5). Although the investigation of cyanate sources
demonstrated that all of them were effective for this
transformation, it was found that the KOCN is the best cyanate
source for the formation of the desired product under these
reaction conditions (Table 1, entries 23–24). Furthermore,
temperature (Table S1) and reaction time (Table S2) on the
model reaction were carefully investigated.
To find the proper conditions, phenol (1a) was selected as a
model phenolic compound which initially activated by TCT to
provide the corresponding 2,4,6-triphenoxy-1,3,5-triazine (2a).
The 2,4,6-triphenyl-1,3,5-triazine (2a) was readily prepared
according to the previously reported procedure (see the ESI).[18]
Compound 2a was then reacted with different sources of
cyanate anions in the presence of various nickel catalytic
systems for the in-situ formation of phenyl isocyanate followed
by the addition of n-propanol to produce n-propyl
N-phenylcarbamate (3aa) as the desired product (Table 1).
Table 1. Optimization of reaction parameters for the synthesis of propyl
N-phenylcarbamate (3aa).a
To show the versatility of the nominal catalytic system, the
protocol was further checked with various derivatives of
phenol-based compounds (Table 2). As shown in the table,
phenol A, anisole B, phenyl acetate C, and tert-butyl phenyl
carbonate D did not proceed with the reaction and almost
remained intact. However, under identical conditions, the use of
the related sulfamate, triflate, tosylate and phosphate
compounds (E-H) successfully promoted the reaction and the
obtained yields were 43%, 58%, 49%, and 52%, respectively.
Entry
1
2
3
4
5
6
7
8
[Ni](X mol%)
Ligand(Y mol%)
MOCN yield (%)b
NiCl2 (10 mol%)
NiBr2 (10 mol%)
Ni(OAc)2 (10 mol%)
Ni(acac)2 (10 mol%)
Ni(COD)2 (10 mol%)
--
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%) 1,10-Phen (10 mol%)
Dppf (10 mol%)
Dppf (10 mol%)
Dppf (10 mol%)
Dppf (10 mol%)
Dppf (10 mol%)
Dppf (10 mol%)
--
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
KOCN
NaOCN
NH4OCN
0
0
43
46
86
0
Table 2. Optimization of reaction parameters for the synthesis of propyl
N-phenylcarbamate (3aa).a
0
Glyme (10 mol%)
28
24
29
30
27
33
42
56
62
68
63
76
86
73
84
81
79
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
Ni(COD)2 (10 mol%) 2,2ʹ-Bipy (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%)
Ph3P (10 mol%)
PCy3 (10 mol%)
P(tBu)3 (10 mol%)
Ni(COD)2 (10 mol%) XantPhos (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (5 mol%)
Ni(COD)2 (8 mol%)
Ni(COD)2 (15 mol%)
Ni(COD)2 (8 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2 (10 mol%)
Ni(COD)2(10 mol%)
Dcype (10 mol%)
Dppe (10 mol%)
Dppp (10 mol%)
Dppf (5 mol%)
Dppf (8 mol%)
Dppf (15 mol%)
Dppf (15 mol%)
Dppf (20 mol%)
Dppf (10 mol%)
Dppf (10 mol%)
A: 1.0 mmol
3aa: 0 %a
B: 1.0 mmol
3aa: 0 %a
C: 1.0 mmol
3aa: 0 %a
D: 1.0 mmol
3aa: 0 %a
E: 1.0 mmol
3aa: 43 %a
F: 1.0 mmol
3aa: 58 %a
[a] Reaction conditions. Step 1: phenol (1.1 mmol), NaH (1.2 mmol) in dry 1,4-
dioxane (3 mL) stirred for 1h at room temperature; Step 2: TCT (0.33 mmol)
was added to the reaction mixture and stirred for 10 h at 100 °C; Step 3: Ni
catalyst (X mol %), ligand (Y mol %), MOCN (2 mmol) and n-propanol (2
mmol) was added to the reaction mixture and stirred for 12h at 100 °C.
[b] Isolated yield, an average of 3 runs.
G: 1.0 mmol
3aa: 49 %a
H: 1.0 mmol
3aa: 52 %a
I: 0.3 mmol
3aa: 86 %a
[a] Isolated yield, an average of 3 runs.
Subsequently, to find the best catalytic system, the model
reaction
was
tested
by
using
10
mol%
of
Interestingly, when compound 2,4,6-triphenyl-1,3,5-triazine (I)
was used as the starting material, the increase in the product
yield up to 86% was observed. The data confirm the benefits of
using the TAT as the phenol-based electrophile respect to the
others for the preparation of N-aryl carbamates (Table 2).
Having established efficient conditions for the in-situ preparation
of aryl isocyanate from the activated aryl alcohol toward
carbamate formation, we next explored the substrate scope of
the present protocol with different varieties of TAT substrates
and alcohols (Table 3).
1,10-bis(diphenylphosphino)ferrocene (Dppf) as the ligand and
different Ni(II) catalysts (10 mol%) (Table 1, entries 1–5).
Unfortunately, the model reaction did not proceed with NiCl2 and
NiBr2 (Table 1, entries 1–2). The moderate yields of n-propyl
N-phenylcarbamate (3aa) were observed when Ni(OAc)2 and
Ni(acac)2 used as the catalyst (Table 1, entries 3 and 4).
Fortunately, the yield of the desired product was improved to
86% in the presence of Ni(COD)2 (Table 1, entry 5). The
experiments showed that both Ni catalyst and ligand are
necessary for the reaction (Table 1, entries 6–7). Moreover, the
important effect of the ligand on the reaction efficiency was
At first, we screened the reaction of different phenol substrates
and found that phenol containing both electron-donating and
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10.1002/cctc.202000876
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withdrawing groups provided the carbamate product in good to
excellent yields (Table 3, compounds 3aa-am). However,
substitution at ortho-position in the phenols showed a reduced
yield of the desired carbamates due to the diminished yield of
the aryl isocyanate (Table 3, compounds 3ad-ae). Besides, the
naphthalic alcohols could also provide the corresponding
carbamates in good yields (Table 3, compounds 3an-ao).
Interestingly, heteroaryl alcohols were employed and carbamate
products obtained in satisfactory yields (Table 3, compounds
3ap-as). Next, we sought the possibility of applying other
alcohols as nucleophiles on the synthesis of carbamates under
the optimized reaction conditions. Intestinally, the aliphatic,
allylic, and benzylic alcohols generally performed well in this
transformation towards the production of the desired carbamates
in good to excellent yields (Table, compounds 3at-bf). The
sterically hindered substrates such as L-(-)-menthol and tert-
butyl alcohol gave corresponding products in slightly lower yields
(Table 3, compounds 3bb-bc). In the synthesis of carbamates
from aryl isocyanates, the aromatic alcohols could not react
similarly to the aliphatic alcohols which might be due to their
lower nucleophilicity. On the other hand, the increase in the
amount of aryl isocyanate in the reaction media could lead to the
formation of isocyanurate as a side product.
Table 4. Activation of the C–O bond in aryl-alcohols using TCT reagent for the Ni-catalyzed synthesis of N-aryl carbamates.a
3aa; 86%a
3ab; 88%a
3af; 87%a
3aj; 83%a
3ac; 85%a
3ag; 89%a
3ak; 84%a
3ad; 80%a
O
Ph
O
n-Pr
N
H
O
3ae; 74%a
3ai; 80%a
3ah; 88%a
3al; 81%a
O
S
n-Pr
N
H
O
3an; 80%a
3ar; 81%a
3av; 90%a
3ao; 82%a
3as; 78%a
3aw; 88%a
3ap; 79%a
3am; 83%a
3aq; 77%a
3au; 89%a
3at; 90%a
3ax; 87%a
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3az; 82%a
3ba; 85%a
3ay; 83%a
3bb; 64%a
O
Ph
N
H
O
3bc; 66%a
3bd; 82%a
3be; 81%a
3bf; 73%a
[a] Isolated yield, an average of 3 runs.
To understand the stability of the [Ni(COD)(dppf)] catalytic
Ni-catalytic systems,[22] the plausible mechanism for this protocol
is proposed as illustrated in Scheme 2.
[20]
system
during the reaction condition, as a case study, we
examined 31P-NMR spectroscopy of the complex 1 before and
after increasing temperature up to 100 oC at different times
under N2 atmosphere.
It is known that the Ni(COD)2 catalyst in the presence of dppf
ligand forms the Ni-complex (A) due to the high steric demand of
the dppf ligand. Subsequently, the oxidative addition of TAT
electrophile to the Ni-complex (A) led to the formation of
Ni(II)-complex (B) as an intermediate. The next step involves
rapid coordination/ligand exchange of the intermediate (B) by a
cyanate ion to form the intermediate (C). This intermediate
through a reductive elimination process results in the formation
of (hetero)aryl isocyanate and regenerating the Ni-complex (A).
It should be noted that the C-O bond cleavage takes place
selectively at aryl C-O [18, 22] and no product with respect to the
cleavage of the triazine C-O was observed. Finally, the alcohol
can attack to the in-situ produced (hetero)aryl isocyanate to
afford the corresponding carbamate. Moreover, the regenerated
Ni-complex (A) is ready to concurrently take part in the next
cycle.
Figure 1. Partial 31P NMR of complex 1([Ni(COD)(dppf)] ) in toluene-d8 at
different times. Sample conditions: before heating at 100 oC (A), after 2 hours
(B) and after 5 h(C). Ph3PO is an internal standard.
As shown in figure 1A, the mixture of complex 1 and Ph3PO (as
an internal standard) at room temperature presented two peaks
in ~25 ppm and ~34 ppm. These two peaks were also observed
in 31P NMR of the mixture after 2 hours at 100 oC, along with two
small peaks in around ~9 ppm and ~31 ppm (Figure 1B). This
spectral pattern was further clearly observed in 31P NMR
spectrum after 5 hours at 100 oC (Figure 1C). Based on this
finding and the above-mentioned results, complex 1 was stable
enough to drive the reaction to the desired product. The results
are consistent well with previously reported stability studies of
the complex (A).[20-21] It has been reported that a series of
comproportionation and disproportionation events can occur
during the organic transformations.[20]
It should be noted that the modulation of the ligand sphere at Ni
centers affect the oxidation state and reactivity of the elementary
catalytic steps.[21] In accordance with the previously reported
Scheme 2. Proposed mechanism for nickel-catalyzed synthesis of
N-(hetero)aryl carbamates from potassium isocyanate and activated phenol
with TCT.
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10.1002/cctc.202000876
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completion of the reaction, ethyl acetate (3×10 mL) was added
and the mixture was filtered. The organic phase was washed
with water (2×10 mL) and dried over anhydrous Na2SO4. The
solvent (EtOAc) was removed under reduced pressure and the
product was purified by column chromatography on silica gel
(petroleum ether and ethyl acetate, 8:2) and characterized. The
isolated pure products were obtained in excellent to moderate
yields.
Conclusions
In summary, we have designed and developed an efficient
domino strategy for the one-pot conversion of phenolic
compounds to their corresponding N-aryl carbamates. The aryl
isocyanate intermediates are in-situ formed from the nickel-
catalyzed coupling of cyanate anions with electrophilic TAT
reagents via C-O activation. Triaryloxytriazine is used as an
alternative for the aryl halides for the carbamate synthesis.
Notably, the method allows the one-pot preparation of
electrophilic TAT reagents from the cheap and accessible
(hetero)aryl alcohols in the presence of TCT without the need of
the isolation and purification process. The features of this
method such as the broad substrate scope and the use of green
and inexpensive starting materials make it a viable strategy for
the industrial and pharmaceutical applications. We believe that
the method would open a new avenue for the synthesis of
various organic compounds from alcohols and phenols as
starting materials.
Propyl phenylcarbamate(3aa):White crystal (0.1541 gr, 86%
yield); mp: 50-51°C. IR (KBr); 3317 (s), 3138 (m), 3058 (m),
3019 (vw), 2985 (s), 2974 (s), 1704 (vs), 1597 (s), 1544 (s),
1447 (s), 1376 (m), 1317 (vs), 1304 (m), 1238 (vs), 1177 (m),
1159 (w), 1121 (s), 1080 (m), 1054 (s), 1027 (m), 995 (vw), 966
(w), 905 (s), 855 (vw), 845 (vw), 823 (w), 761 (s), 747 (s), 690
(s), 508 (m) cm-1. 1H-NMR (250 MHz, CDCl3):δ= 7.26 (m, 4H),
6.97 (m, 1H), 6.64 (s, br, 1H, NH), 4.05 (t, J = 7.5 Hz, 2H), 1.62
(sext, J = 7.5 Hz, 2H), 0.90 (t, J = 7.5 Hz, 3H) ppm. 13C-NMR (63
MHz, CDCl3):δ =153.74, 137.98, 129.01, 123.30, 118.63, 66.83,
22.26, 10.34 ppm. MS Calcdm/z 179.22, Found 179. Anal. Calcd
for C10H13NO2: C, 67.02; H, 7.31; N, 7.82%. Found: C, 66.97; H,
7.32; N, 7.86%.
The data for all the other prepared carbamates can be found in
the SupportingInformation.
Experimental Section
General experimental:
Acknowledgments
Chemicals were obtained from Sigma-Aldrich and Merck.
Column chromatography was performed using silica gel from
Macherey-Nagel (60 M, 0.04–0.063 mm). The products were
characterized by spectral and physical data such as NMR, FT-IR,
MS, CHNS and melting point. Melting points were recorded by
Electrothermal 9100. Fourier transforms infrared (FTIR) spectra
were obtained using a Shimadzu FT-IR 8300 spectrophotometer.
1H and 13C NMR spectra were recorded with Bruker Avance
DPX 250MHz instruments with Me4Si or solvent resonance as
the internal standard. 1H NMR spectroscopic data are reported
as follows: chemical shift, multiplicity (s = singlet, d = doublet, t =
triplet, q= quartet, quint = quintet, sext = sextet, sept = septet, br.
= broad, m = multiplet), coupling constants (Hz), and integration.
31P NMR spectra were recorded on a Bruker Avance DRX 400
MHz. The mass spectra were recorded on a Shimadzu GC-MS
QP 1000 EX instrument. The C, H, N and S elemental analyses
were carried out by using a Thermofinigan Flash EA-1112
CHNSO rapid elemental analyzer. Determination of the purity of
the substrate and monitoring of the reaction were accomplished
by thin-layer chromatography (TLC) on a silica-gel polygram
SILG/UV 254 plates.
We gratefully acknowledge the partial financial support of this
study by the research councils of Shiraz University and
University of Zabol (UOZ-GR-9618-53) and a grant from the Iran
National Science Foundation.
Keywords: Carbamate • C-O bond activation • Phenol • Nickel
catalyst • Aryl isocyanate • Cyanuric Chloride.
[1]
a) J. Wu, M. Pistolozzi, S. Liu, and W. Tan, Bioorg. Med. Chem. 2020,
28, 115324; b) W. Chen-Hsien, Synthesis 1981, 622; c) T. Mizuno, I.
Nishiguchi, T. Okushi and T. Hirashima, Tetrahedron Lett. 1991, 32,
6867; d) A. Goel, S. J. Mazur, R. J. Fattah, T. L. Hartmann, J. A. Turpin,
M. Huang, W. G. Rice, E. Appella and J. K. Inman, Bioorg. Med.
Chem.Lett. 2002, 12, 767; e) A.R. Sardarian and I.D. Inaloo, RSC Adv.
2015, 5, 76626; f) M. Krátký, O. Janďourek, Z. Baranyai, E. Novotná, J.
Stolaříková, S. Bősze, and J. Vinšová, Eur. J. Med. Chem. 2019, 181,
111578.
[2]
[3]
[4]
a) L.W. Xu, C.G. Xia and X.X. Hu, Chem. Commun. 2003, 2570; b) V.
Murugesan, V. Balakrishnan and R. Rasappan, J. Catal. 2019, 377,
293; c) L. Hie, S.D. Ramgren, T. Mesganaw, and N.K. Garg, Org. lett.
2012, 14, 4182; d) I.D. Inaloo and S. Majnooni, New J. Chem. 2018, 42,
13249; e) H. Sumiyoshi, T. Shimizu, M. Katoh, Y. Baba and M.
Sodeoka, Org. lett. 2002, 4, 3923.
General Procedure for the activation of the C–O bond in
aryl-alcohols using TCT reagent for the synthesis of N-aryl
carbamates (3aa-3bf):
In a flask, NaH (1.2 mmol) was added to a stirring mixture of
phenol (1.1 mmol) in dry 1,4-dioxane (3 mL) at room
temperature and stirred for 1h. Then, TCT (0.33 mmol) was
added and the mixture was stirred for 10 h at 100 °C which
delivered TAT in good yield. Then, the reaction was cooled
down to room temperature and Ni(COD)2 (10 mol%) and dppf
(10 mol%) were weighed and added in a glove box. Then, the
potassium cyanate (2 mmol) and alcohol (2 mmol) was added;
the mixture was stirred at 100 °C for 12 h under ni trogen
atmosphere. The reaction was monitored by TLC. After
a) J. S. Nowick, N. A. Powell, T. M. Nguyen and G. Noronha, J. Org.
Chem. 1992, 57, 7364; b) P. Majer and R. S. Randad, J. Org. Chem.
1994, 59, 1937; c) R. A. Batey, V. Santhakumar, C. Yoshina-Ishii and S.
D. Taylor, Tetrahedron Lett. 1998, 39, 6267; d) ID. Inaloo, S. Majnooni
and M. Esmaeilpour, Eur. J. Org. Chem. 2018, 3481; e) I. Dindarloo
Inaloo and S. Majnooni, ChemistrySelect. 2019, 4, 7811.
a) X. Zhao, S. Yang, S. Ebrahimiasl, S. Arshadi and A. Hosseinian, J.
CO2 Util. 2019, 33, 37; b) M. Zhang, X. Zhao and S. Zheng, Chem.
Commun. 2014, 50, 4455; c) Y. Peng, J. Liu, C. Qi, G. Yuan, J. Li and
H. Jiang, Chem. Commun. 2017, 53, 2665; d) I.D. Inaloo and S.
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FULL PAPER
Majnooni, New J. Chem. 2019, 43, 11275; e) R. Khatun, S. Biswas, S.
Zhang and D. Ma, Adv. Synth. Catal. 2012, 354, 2443; d) E.V.
Vinogradova, N.H. Park, B.P. Fors, and S.L. Buchwald, Org. lett. 2013,
15, 1394; e) S.V. Kumar and D. Ma, J. Org. Chem., 2018, 83, 2706.
[14] a) R. Takise, K. Muto, J. Yamaguchi and K. Itami, Angew. Chem. Int.
Ed. 2014, 53, 6791; b) H. Zeng, Z. Qiu, A. Domínguez-Huerta, Z.
Hearne, Z. Chen and C.-J. Li, ACS Catal. 2017, 7, 510; c) M. Tobisu
and N. Chatani, Top. Curr. Chem. 2016, 374, 41.
Islam, I. H. Biswas, S. Riyajuddin, K. Ghosh, S. M. Islam,
ChemCatChem 2019, 11, 1303; f) M. Tamura, A. Miura, M. Honda, Y.
Gu, Y. Nakagawa, K. Tomishige, ChemCatChem 2018, 10, 4821.
a) L. Ren and N. Jiao, Chem. Commun. 2014, 50, 3706; b) A. Iturmendi,
M. Iglesias, J. Munárriz, V. Polo, J.J. Pérez-Torrente and L.A. Oro,
Chem. Commun. 2017, 53, 404; c) I.D. Inaloo and S. Majnooni, Eur. J.
Org. Chem. 2019, 6359; d) F. Shi and Y. Deng, Chem. Commun. 2001,
443.
[5]
[15] a) M. Tobisu and N. Chatani, Acc. Chem. Res. 2015, 48, 1717; b) J.
Cornella, C. Zarate and R. Martin, Chem. Soc. Rev. 2014, 43, 8081.
[16] a) A. Correa and R. Martin, J. Am. Chem. Soc. 2014, 136, 7253; b) Y.
Gu and R. Martín, Angew. Chem., Int. Ed. Engl. 2017, 56, 3187; c) M.
Tobisu, T. Takahira, A. Ohtsuki and N. Chatani, Org. Lett. 2015, 17,
680.
[6]
[7]
[8]
[9]
a) A. Wurtz, C. R.Acad. Sci. Paris. 1848, 27, 242; b) E. Delebecq, J.P.
Pascault, B. Boutevin, and F. Ganachaud, Chem. Rev. 2013, 113, 80;
c) A.R. Sardarian, I. Dindarloo Inaloo, A.R. Modarresi-Alam, E.
Kleinpeter and U. Schilde, J. Org. Chem. 2019, 84, 1748.
a) J.H. Saunders and R.J. Slocombe, Chem. Rev. 1948, 43, 203; b)
M.S. Rolph, A.L. Markowska, C.N. Warriner and R.K. O'Reilly, Polym.
Chem. 2016, 7, 7351; c) Y. Ren and S.A. Rousseaux, J. Org. Chem.
2018, 83, 913.
[17] E. V. Vinogradova, B. P. Fors, and S. L.Buchwald, J. Am. Chem. Soc.
2012, 134, 11132.
[18] a) N. Iranpoor and F. Panahi, Adv. Synth. Catal. 2014, 356, 3067; b)
M.M. Heravi, F. Panahi and N. Iranpoor, Org. Lett. 2018, 20, 2753; c) N.
Iranpoor and F. Panahi, Org. Lett. 2015, 17, 214; d) S. Rahimi, F.
Panahi, M. Bahmani and N. Iranpoor, J. Org. Chem. 2018, 83, 973.
[19] I. DindarlooInaloo, S. Majnooni, H. Eslahi and M. Esmaeilpour, ACS
Omega 2020, 5, 7406.
a) S. Li, R. Khan, X. Zhang, Y. Yang, Z. Wang, Y. Zhan, Y. Dai, Y.E.
Liu and B. Fan, Org. Biomol. Chem. 2019, 17, 5891; b) J. Bruffaerts, N.
Von Wolff, Y. Diskin-Posner, Y. Ben-David and D. Milstein, J. Am.
Chem. Soc. 2019, 141, 16486.
a) A. W. Hofmann, Ber. 1870, 3, 653; b) A. W. Hofmann, Ber. 1870, 3,
765; c) A. W. Hofmann, Ber. 1871, 4, 246; d) A. W. Hofmann, Ber. 1885,
18, 765; e) P. Gogoi and D. Konwar, Tetrahedron Lett. 2007, 48, 531; f)
M. J. Burk and J. G. Allen, J. Org. Chem. 1997, 62, 7054; g) Y.
Matsumura, T. Maki and Y. Satoh, Tetrahedron Lett. 1997, 38, 8879.
[20] a) G. Yin, I. Kalvet, U. Englert and F. J. Schoenebeck, J. Am. Chem.
Soc. 2015, 137, 4164; b) L. M. Guard, M. Mohadjer Beromi, G. W.
Brudvig, N. Hazari and D. J. Vinyard, Angew. Chem., Int. Ed. 2015, 54,
13352; c) M. Mohadjer Beromi, A. Nova, D. Balcells, A. M. Brasacchio,
G. W. Brudvig, L. M. Guard, N. Hazari and D. J.Vinyard, J. Am. Chem.
Soc. 2017, 139, 922.
[10] a) E. F. V. Scriven and K. Turnbull, Chem. Rev. 1988, 88, 297; b)T.
Curtius, Chem. Ber. 1890, 23, 3029; c) T. Curtius, J. Prakt. Chem. 1894,
50, 275.
[21] a) S. Bajo, G. Laidlaw, A.R. Kennedy, S. Sproules and D.J. Nelson,
Organometallics. 2017, 36, 1662; b) R. Sawaki, Y. Sato and M. Mori,
Org. Lett. 2004, 6, 1131; c) A. Cooper, D. Leonard, S. Bajo, P.M.
Burton and D.J. Nelson, Chem. Sci. 2020, 11, 1905; d) A.B. Dürr, G.
Yin, I. Kalvet, F. Napoly and F. Schoenebeck, Chem. Sci. 2016, 7, 1076.
[22] a) A. R. Ehle, Q. Zho and M. P. Watson, Org. Lett. 2012, 14, 1202, b) E.
Etemadi-Davan and N. Iranpoor, Chem. Commun. 2017, 53, 12794; c)
M.M. Heravi, F. Panahi and N. Iranpoor, Chem. Commun. 2020, 56,
1992; d) B. Wang, Q. Zhang, J. Jiang, H. Yu, Y. Fu, Chem. Eur. J. 2017,
23, 17249.
[11] a) E. C. Franklin, Chem. Rev. 1934, 14, 219; b) S. Yoganathan and S. J.
Miller, Org. Lett. 2013, 15, 602; c) L. Bauer and O. Exner, Angew.
Chem., Int. Ed. Engl. 1974, 13, 376; d) H. L. Yale, Chem. Rev. 1943, 33,
209; e) P. Dubé, N. F. F. Nathel, M. Vetelino, M. Couturier, C. L.
Aboussafy, S. Pichette, M. L. Jorgensen and M. Hardink, Org. Lett.
2009, 11, 5622.
[12] H. Wolff, Org. React. 1946, 3, 307.
[13] a) I. Tkatchenko, R. Jaouhari, M. Bonnet, G. Dawkins and S. Lecolier,
FR2575467, 1986; U.S. Patent 4749806, 1988; b) E. Kianmehr and M.
H. Baghersad, Adv. Synth. Catal. 2011, 353, 2599; c) X. Yang, Y.
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10.1002/cctc.202000876
ChemCatChem
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In this work, a simple and efficient domino reaction has been designed and used for the synthesis of N-(hetero)aryl carbamates by
the in-situ formation of (hetero)aryl isocyanates and their reaction with alcohols in the presence of a nickel catalyst. The C-O bond
was activated through the reaction of phenol with cyanuric chloride. This strategy provides a practical access to N-(hetero)aryl
carbamates in good yields with high functional groups compatibility.
This article is protected by copyright. All rights reserved.