Orito et al.
under high pressure at 131, 90, or 66 atm. Carbonylations by
Pd catalyses have been extensively studied since Tsuji reported
in 1966 the first Pd-catalyzed carbonylation of amines,13a in
which PdCl2 was used under CO at 100 kg/cm2 and at 180 °C
to give a mixture of N,N′-didecylurea and N,N′-didecyloxamide
from decylamine in benzene. Methods for oxidative carbonyla-
tion by using PdCl2 with oxidant O2 and/or CuX or CuX2 have
been developed for preparation of ureas,13g,m,o carbamates,13h,n
and oxamides or related double carbonyl compounds.13k,l,n,p
A
method for preparing cyclic mono- and dicarbonyl compounds
and their chemical transformations were reported in detail by
Murahashi.13u
Methods for oxidative carbonylation of alkylamines or aniline
using a combination of Pd/C and NaI in the presence of O2,
which provided ureas and/or carbamates, were reported by
Fukuoka13f and Chaudhari.13o,r,s Gabriele’s procedure using PdI2
and O2 led to good formation of ureas, carbamates, and their
cyclic derivatives.16
It was reported by Heck in 1974 that carbonylation using
aromatic nitro compounds and aromatic primary amines under
1 atm of CO produced a mixture of N,N′-diarylureas in the
presence of catalytic amounts of PdBr2(PPh3)2, Et4NCl, and
n-Bu3N. Under a compressed pressure of CO, unsymmetrical
ureas were selectively prepared by a Se-catalyzed oxidative-
reductive carbonylation similarly using nitrobenzene derivatives
and primary or secondary amines, in which reduction of the
nitro group into an amino group prior to the carbonylation was
involved, as reported by Lu.3l-p Gabriele’s oxidative carbon-
ylation with PdI2 mentioned above also gave N,N,N′-trisubsti-
tuted ureas from primary and secondary amines under CO at
60 atm of pressure.16d
Two Pd-Zr catalytic systems have been employed in the
oxidative carbonylation of aniline and alkylamines.14 One [Pd/
ZrO2-SO42-/CO (3.5 MPa)/O2 (0.5 MPa)] reported by Deng14b
gave N-phenyl-N′-alkylureas.
Carbonylations of primary or secondary alkylamines and
primary or secondary R,ω-diamines were carried out using
W(CO)6 as a catalyst and I2 as an oxidant at 60-100 atm of
CO to afford symmetrical dialkyl- or tetraalkylureas and cyclic
ureas. The method was applied to the synthesis of seven-
membered cyclic ureas related to HIV protease inhibitors.17h
Gold also produced diarylureas and N-arylcarbamates by
oxidative carbonylation using a polymer-immobilized Au cata-
lyst prepared from HAuCl4‚4H2O.19
(4) Tl: Sonoda, N.; Yasuhara, T.; Kondo, K.; Ikeda, T.; Tsutsumi, S.
Bull. Chem. Soc. Jpn. 1981, 54, 1460.
(5) Hg: Tsuji, J.; Iwamoto, N. Japan Patent 6904096; Chem. Abstr. 1969,
71, 12792. Nefedov, B. R.; Sergeeva, N. S.; Eidus, Ya. T. IzV. Akad. Nauk.
SSSR, Khim. 1973, 807; Chem. Abstr. 1973, 79, 31813.
(6) Mn: (a) Calderazzo, F. Inorg. Chem. 1965, 4, 293. (b) Dombek, D.;
Angelici, R. J. J. Organomet. Chem. 1977, 134, 203. (c) Srivastava, S. C.;
Shrimal, A. K.; Srivastava, A. J. Organomet. Chem. 1991, 414, 65. (d) Li,
K.-T.; Peng, Y.-J. J. Catal. 1993, 143, 631.
(7) Fe: (a) Dombeck, B. K.; Eidus, Ya. T. IzV. Akad. Nauk. SSSR, Khim.
1976, 1782; Chem. Abstr. 1977, 86, 16056. German Patent 1170396; Chem.
Abstr. 1964, 61, 2979. (b) Sampson, H. J., Jr. U.S. Patent 2589289; Chem.
Abstr. 1952, 46, 11234. (c) Dombek, B. D.; Angelici, R. J. J. Catal. 1977,
48, 433.
(8) Co: (a) Sternberg, H. W.; Wender, I.; Friedel, R. A.; Orchin, M. J.
Am. Chem. Soc. 1953, 75, 3148. (b) Rosenthal, A. Can. J. Chem. 1962, 40,
1718. (c) Benedini, F.; Nali, M.; Rindone, B.; Tollari, S.; Cenini, S.; Monica,
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Tollari, S.; Chioccara, F. J. Mol. Catal. 1990, 60, 41.
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Zh. 1961, 5, 54; Chem. Abstr. 1962, 57, 8413. (b) Aliev, Ya. Yu.; Romanova,
I. B. Neftekhim., Akad. Nauk Turkm., SSR 1963, 204; Chem. Abstr. 1964,
61, 6913. (c) Martin, W. E.; Farona, M. F. J. Organomet. Chem. 1981,
206, 393. (d) Hoberg, H.; Fan˜ana´s, F. J.; Riegel, H. J. J. Organomet. Chem.
1983, 254, 267. (e) Giannoccaro, P.; Nobile, C. F.; Mastrorilli, P.; Ravasio,
N. J. Organomet. Chem. 1991, 419, 251.
(10) Cu: Brackman, W. Discuss. Faraday Soc. 1968, 122.
(11) Ru: (a) Byerley, J. J.; Rempel, G. L.; Takebe, N. J. Chem. Soc.,
Chem. Commun. 1971, 1482. Lassau, C.; Cheuvin, Y.; Lefevro, G. Ger.
Offen. 1902560; Chem. Abstr. 1970, 72, 21358. Yamahara, T.; Takamatsu,
S.; Hirose, K. Japan Kokai 72 34341; Chem. Abstr. 1973, 78, 43087. (b)
With Rh, Pt and Ir: Fukuoka, S.; Chono, M.; Kohno, M. J. Org. Chem.
1984, 49, 1458. (c) Taqui Khan, M. M.; Halligudi, S. B.; Abdi, S. H. R.;
Shukla, S. J. Mol. Catal. 1988, 48, 25. (d) Taqui Khan, M. M.; Halligudi,
S. B.; Shukla, S.; Abdi, S. H. R. J. Mol. Catal. 1989, 51, 129. (e) With Rh,
Mulla, S. A. R.; Gupte, S. P.; Chaudhari, R. V. J. Mol. Catal. 1991, 67,
L7. (f) With Rh, Mulla, S. A. R.; Rode, C. V.; Kelkar, A. A.; Gupte, S. P.
J. Mol. Catal. A 1997, 122, 103. (g) Kondo, T.; Kotachi, S.; Tsuji, Y.;
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(13) Pd: (a) Tsuji, J.; Iwamoto, N. Chem. Commun. 1966, 380. (b)
Schoenberg, A.; Heck, R. F. J. Org. Chem. 1974, 39, 3327. Dieck, H. A.;
Laine, R. M.; Heck, R. F. J. Org. Chem. 1975, 40, 2819. (c) Ozawa, F.;
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Yamamoto, A. Organometallics 1984, 3, 683. (e) Ozawa, F.; Sugimoto,
T.; Yamamoto, T.; Yamamoto, A. Organometallics 1984, 3, 692. (f)
Fukuoka, S.; Chono, M.; Kohno, M. J. Chem. Soc., Chem. Commun. 1984,
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Methods for carbonylation of amines in an atmosphere of
pressure to ureas have been limited to oxidative carbonylation
with Se,3a,f CuCl2,10 PdCl2,13h,m Pd(OAc)2 on clay,13q and a
homogeneous catalyst, [Ru(CO)3I3]NBu4,11f to oxidative-
reductive carbonylation with PdBr2(PPh3)2 using nitrobenzene
and anilines,13b and to electrochemical carbonylation with PdCl2-
(PPh3)2-Cu(OAc)2 or Pd(OAc)2(PPh3)2-NaOAc.15c
15a
(16) PdI2: (a) Gabriele, B.; Salerno, G.; Brindisi, D.; Costa, M.; Chiusoli,
G. P. Org. Lett. 2000, 2, 625. (b) Gabriele, B.; Mancuso, R.; Salerno, G.;
Costa, M. J. Org. Chem. 2003, 68, 601. (c) Gabriele, B.; Mancuso, R.;
Salerno, G.; Costa, M. Chem. Commun. 2003, 406. (d) Gabriele, B.; Salerno,
G.; Mancuso, R.; Costa, M. J. Org. Chem. 2004, 69, 4741.
(17) W: (a) Patterson, J. A.; Atwell, H. V. U.S. Patent 2993931; Chem.
Abstr. 1962, 56, 1392. (b) German Patent 1158494; Chem. Abstr. 1964,
61, 11900. (c) German Patent 1163311; Chem. Abstr. 1964, 60, 15744. (d)
McCusker, J. E.; Grasso, C. A.; Main, A. D.; McElwee-White, L. Org.
Lett. 1999, 1, 961 (e) McCusker, J. E.; Qian, F.; McElwee-White, L. J.
Mol. Catal. A 2000, 159, 11. (f) McCusker, J. E.; Main, A. D.; Johnson, K.
S.; Grasso, C. A.; McElwee-White, L. J. Org. Chem. 2000, 65, 5216. (g)
Qian, F.; McCusker, J. E.; Zhang, Y.; Main, A. D.; Chlebowski, M.; Kokka,
M.; McElwee-White, L. J. Org. Chem. 2002, 67, 4086. (h) Hylton, K.-G.;
Main, A. D.; McElwee-White, L. J. Org. Chem. 2003, 68, 1615.
(18) Pt: (a) Kucheryavyi. I.; Gorlovskii, D. M.; Al’tshuler, L. N.;
Zinov’ev, G. N.; Karlik, A. B.; Klopina, N. A. USR 371210; Chem. Abstr.
1973, 79, 18161.
(14) Pd on Zr: (a) Giannoccaro, P.; Nobile, C. F.; Moro, G.; Ginestra,
A. La; Ferragina, C.; Massucci, M. A.; Patrono, P. J. Mol. Catal. 1989, 53,
349. (b) Shi, F.; Deng, Y.; SiMa, T.; Yang, H. Tetrahedron Lett. 2001, 42,
2161.
(19) Au: Shi, F.; Y. Deng, Y. J. Catal. 2002, 211, 548.
(15) Pd in electrolytic oxidation: (a) Yang, H.; Deng, Y.; Shi, F. J. Mol.
Catal. A 2001, 176, 73. (b) Chiarotto, I.; Feroci, M. Tetrahedron Lett. 2001,
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(20) For classical methods for preparation of ureic derivatives using
phosgene and other carbonylation reagents and their biological activities,
see Gabriele’s well-reviewed paper, ref 16d and references therein.
5952 J. Org. Chem., Vol. 71, No. 16, 2006