D
Synlett
K. Madankar et al.
Letter
Table 2 (continued)
Entry
Phenol 1
RNHR′ 4
Product 5
Yield (%)
62
Mp (°C)
72–7412c
OH
13
14
15
NH2
NH2
NH2
5b
Cl
OH
5e
60
71
100-10219
86–8912c
MeO
OH
5f
Me
a
Reaction conditions: 1 (1.0 mmol), 4 (1.6 mmol), DCID (1.0 mmol), CuI (20 mol%), Et
Structures of compounds 5i, 5j, and 5k were confirmed by NMR spectra (see Supporting Information).
3
N (1.0 mmol) in MeCN (5 mL) at 80 °C.
b
In conclusion, we have developed a novel modified
cross-coupling of phenols with various aromatic and ali-
(7) Li, B.-J.; Yu, D.-G.; Sun, C.-L.; Shi, Z.-J. Chem. Eur. J. 2011, 17,
728.
8) So, C. M.; Kwong, F. Y. Chem. Soc. Rev. 2011, 40, 4963.
1
(
phatic amines using dichloroimidazolidinedione (DCID) as
a new and efficient reagent in the presence of copper(I).24–27
(9) Cornella, J.; Zarate, C.; Martin, R. Chem. Soc. Rev. 2014, 43, 8081.
10) Bisz, E.; Szostak, M. ChemSusChem 2017, 10, 3964.
11) Tobisu, M.; Chatani, N. Top. Curr. Chem. 2016, 374, 41.
12) (a) Panahi, L.; Naimi-Jamal, M. R.; Mokhtari, J.; Morsali, A.
Microporous and Mesoporous Materials 2016, 244, 208.
(b) Tahmasebi, S.; Khosravi, A.; Mokhtari, J.; Naimi-Jamal, M. R.;
Panahi, L. J. Organomet. Chem. 2017, 853, 35. (c) Khosravi, A.;
Tahmasebi, S.; Mokhtari, J.; Naimi-Jamal, M. R.; Panahi, L. RSC
Adv. 2017, 7, 46022.
(
(
(
Various substituted aromatic amines were obtained in good
to excellent yields. The Ph-OMCID intermediate 3 is not iso-
lated in this method and is therefore much more conve-
nient and useful compared to the known reported methods.
Investigations regarding the scope and application of this
reagent (DCID) and further mechanistic studies are current-
ly in progress.
(
13) Gao, Y.; Liu, J.; Li, Z.; Guo, T.; Xu, S.; Zhu, H.; Wei, F.; Chen, S.;
Gebru, H.; Guo, K. J. Org. Chem. 2018, 83, 2040.
(
(
14) Schilter, D.; Bielawski, C. W. Org. Synth. 2016, 93, 413.
15) Li, J.; He, S.; Fu, H.; Chen, X.; Tang, M.; Zhang, D.; Wang, B. Res.
Chem. Intermed. 2018, 44, 2289.
Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0040-1707224.
(16) Zhao, F.; Li, Y.; Wang, Y.; Zhang, W. X.; Xia, Z. Org. Biomol. Chem.
S
u
p
p
orti
n
g Inform ati
o
n
S
u
p
p
orit
n
g Inform ati
o
n
2014, 12, 3336.
(
(
17) Moerdyk, J. P.; Bielawski, C. W. Chem. Eur. J. 2014, 20, 13487.
18) Madankar, K.; Mokhtari, J.; Mirjafary, Z. Appl. Organomet. Chem.
References and Notes
2020, e5383.
(
1) (a) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M.
Chem. Rev. 2002, 102, 1359. (b) Stanforth, S. P. Tetrahedron
998, 54, 263. (c) Brown, B. R. The Organic Chemistry of Aliphatic
Nitrogen Compounds; Cambridge University: Cambridge, 2004.
(19) Mallia, C. J.; Burton, P. M.; Smith, A. M. R.; Walter, G. C.;
Baxendale, I. R. Beilstein J. Org. Chem. 2016, 12, 1598.
(20) Xu, H.; Wolf, C. Chem. Commun. 2009, 1715.
(21) Dang, T. T.; Shan, S. P.; Ramalingam, B.; Seayad, A. M. RSC Adv.
2015, 5, 42399.
1
(
(
d) McElroy, W. T.; DeShong, P. Tetrahedron 2006, 62, 6945.
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(22) Lee, J.-C.; Wang, M.-G.; Hong, F.-E. Eur. J. Inorg. Chem. 2005, 24,
5011.
9889. (f) Lawrence, S. A. Amines: Synthesis, Properties and Appli-
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3
443.
(24) Synthesis of Dichloroimidazolidinedione (DCID, 2)
Compound 2 was synthesized by following Gao et al.,13 with
minor modifications. To N,N′-dicyclohexylcarbodiimine (DCC, 2
g, 1 mmol) in dry dichloromethane (25 mL) at 0 °C was added
oxalyl chloride (0.9 mL, 1.05 mmol) dropwise. The reaction
mixture was stirred for 1 h at room temperature. The solid
material was separated by filtration and washed with cold
dichloromethane. The recrystallization of white solid in ethanol
(
2) (a) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F.;
Stang, P. J., Ed.; Wiley-VCH: Weinheim, 1998. (b) Cross-Coupling
Reactions. A Practical Guide; Miaura, N., Ed.; Springer: Berlin,
2
002. (c) Metal-Catalyzed Cross-Coupling Reactions; de Meijere,
A.; Diederich, F., Ed.; Wiley-VCH: Weinheim, 2004.
3) (a) Fanta, P. E. Synthesis 1974, 9. (b) Castillo, P. R.; Buchwald, S.
L. Chem. Rev. 2016, 116, 12564.
4) (a) Rouhi, A. M. Chem. Eng. News 2004, 82, 49. (b) Corbet, J.-P.;
Mignani, G. Chem. Rev. 2006, 106, 2651.
(
(
(
(
1
yielded DCID (2,5 g, 97%); mp 174–176 °C. HNMR (499.77 MHz,
CDCl ): = 3.97–4.00 (m, 2 H), 2.02–2.10 (m, 4 H, Cy), 1.73–1.87
3
5) (a) Stang, P. J.; Hanack, M.; Subramanian, L. R. Synthesis 1982,
(m, 4 H, Cy), 1.71–1.75 (m, 4 H, Cy), 1.66–1.69 (m, 2 H, Cy),
1.17–1.36 (m, 6 H, Cy) ppm.
85. (b) Ritter, K. Synthesis 1993, 735.
6) (a) Vorbrüggen, H. Synthesis 2008, 1165. (b) Högermeier, J.;
Reissig, H.-U. Adv. Synth. Catal. 2009, 351, 2747.
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