Nucleophilic [3+3]-addition of N-unsubstituted enamine to monocyclic 1H-pyrrole-2,3-diones

Full text of DOI:10.1134/S1070428008050278

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 5, pp. 772−773. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © E.S. Denislamova, Yu.N. Bannikova, A.N. Maslivets, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44,
No. 5, pp. 777−778.
SHORT
COMMUNICATIONS
Nucleophilic [3+3]-Addition of N-Unsubstituted Enamine to
Monocyclic 1H-Pyrrole-2,3-diones
E. S. Denislamova, Yu. N. Bannikova, and A. N. Maslivets
Perm State University, Perm, 614990 Russia
e-mail: koh2@psu.ru
Received November 27, 2007
DOI: 10.1134/S1070428008050278
A reaction is described of substituted 1H-pyrrole-2,3-
diones (methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-
pyrrole-2-carboxylates) with N-alkyl- and N-aryl-
substituted 3-amino-5,5-dimethyl-2-cyclohexen-1-ones
providing 1-alkyl- and 1-aryl-susbtituted 6,6-dimethyl-
2,4-dioxo-2,3,4,5,6,7-hexahydro-1H-indole-3-spiro-
2'-(1'-aryl-3'-aroyl-4'-hydroxy-5'-oxo-2',5'-dihydro-
1'H-pyrroles) [1, 2]. The reaction proceeds as succes-
sive attacks of β-CH and NH groups of the enamino
fragment of the carbocyclic enamines first on the carbon
atom in the position 2 and then on the carbonyl group
of the methoxycarbonyl moiety (substituent in the
position 2) of pyrrolediones followed by methanol
elimination.
substituted 3-amino-5,5-dimethyl-2-cyclohexen-1-one
(II) taken in a ratio 1:1 performed by boiling in anhydrous
benzene for 1–2 min (to the disappearance of the bright
red color of initial compounds Ia and Ib) we unexpect-
edly obtained methyl 11-aryl-12-benzoyl-9-hydroxy-5,5-
dimethyl-3,10-dioxo-8,11-diazatricyclo[7.2.1.02,7]dodec-
2(7)-ene-1-carboxylates IIIa and IIIb. Spectral char-
acteristics of compounds IIIa and IIIb are close to those
of a model substituted 3,10,13-triazapentacyclo-
[10.7.1.01,10.04,9.014,19]eicosa-4,6,8,14(19)-tetraene,
whose structure was confirmed by XRD analysis [3].
Evidently the bridged compounds IIIa and IIIb
formed by the addition of β-CH and NH2 groups of the
enamino fragment of carbocyclic enamine II to atoms
C2 and C4 respectively of monocyclic pyrrolediones Ia
and Ib.
In reaction of methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-
dihydro-1H-pyrrole-2-carboxylates Ia and Ib with N-un-
Ar
O
COOMe
COPh
Me
Me
H2N
N
O
Ia, Ib
O
II
H2N
HN
Me
Me
Me
Me
MeOCO
Ar
MeOCO
N
Ar
O
N
O
O
H
O
COPh
COPh
OH
OH
IIIa, IIIb
Ar = Ph (a), 4-ClC6H4 (b).
772

NUCLEOPHILIC [3+3]-ADDITION OF N-UNSUBSTITUTED ENAMINE
773
1
The described reaction is a new procedure for
preparation of difficultly accessible functionalized
bridged heterocyclic system of 8,11-diazatricyclo-
[7.2.1.02,7]dodecane and also is the first example of
nucleophilic [3+3]-addition of an enamine to monocyclic
1H-pyrrole-2,3-diones.
(COOMe), 1659 (C10=O), 1623 (COPh). H NMR
spectrum, δ, ppm: 0.72 s (3H, Me), 0.85 s (3H, Me),
1.90, 1.98 d.d (2H, C6H2, J 16.3 Hz), 2.18, 2.30 d.d (2H,
C4H2, J 16.7 Hz), 3.79 s (3H, OMe), 5.11 s (1H, C12H),
6.81 s (1H, OH), 7.47 s (1H, NH), 7.16–7.82 group of
signals (9H, Ph + C6H4). Found, %: C 63.77; H 4.91;
Cl 6.99; N 5.54. C27H25ClN2O6. Calculated, %: C 63.72;
H 4.95; Cl 6.97; N 5.50.
Methyl 12-benzoyl-9-hydroxy-5,5-dimethyl-3,10-
dioxo-11-phenyl-8,11-diazatricyclo-[7.2.1.02,7]dodec-
2(7)-ene-1-carboxylate (IIIa). A solution of 1 mmol of
compound Ia and 1 mmol of enamine II in 5 ml of
anhydrous benzene was boiled for 1 min, then cooled,
the separated precipitate was filtered off. Yield 79%, mp
179–180°C (from ethyl acetate). IR spectrum, ν, cm–1:
3384 (NH), 3090 br (OH), 1751 (C3=O), 1731 (COOMe),
1663 (C10=O), 1630 (COPh). 1H NMR spectrum, δ, ppm:
0.73 s (3H, Me), 0.86 s (3H, Me), 1.91, 1.98 d.d (2H,
C6H2, J 16.1 Hz), 2.18, 2.29 d.d (2H, C4H2, J 16.5 Hz),
3.79 s (3H, OMe), 5.15 s (1H, C12H), 6.75 s (1H, OH),
7.44 s (1H, NH), 7.12–7.82 group of signals (10H, 2Ph).
Found, %: C 68.38; H 5.50; N 5.92. C27H26N2O6.
Calculated, %: C 68.34; H 5.52; N 5.90.
IR spectra of compounds synthesized were recorded
on a spectrophotometer FMS-1201 from mulls in mineral
oil. 1H NMR spectra were registered on a spectrometer
Bruker WP-400 in DMSO-d6, internal reference TMS.
The homogeneity of compounds obtained was proved
by TLC on Silufol plates, eluent ethyl acetate, develop-
ment in iodine vapor.
The study was carried out under financial support of
the Russian Foundation for Basic Research (grant no.
07-03-96036).
REFERENCES
1. Bannikova, Yu.N. and Maslivets, A.N., Khim. Geterotsikl.
Soedin., 2004, p. 124.
2. Bannikova, Yu.N., Maslivets, A.N., and Aliev, Z.G., Zh.
Org. Khim., 2007, vol. 43, p. 1339.
3. Bozdyreva, Ks.S., Maslivets, A.N., and Aliev, Z.G.,
Mendeleev Commun., 2005, p. 163.
Methyl 12-benzoyl-9-hydroxy-5,5-dimethyl-3,10-
dioxo-11-p-chlorophenyl-8,11-diazatricyclo-
[7.2.1.02,7]dodec-2(7)-ene-1-carboxylate (IIIb). Yield
75%, mp 183–184°C (from methanol). IR spectrum, ν,
cm–1: 3330 (NH), 3130 br (OH), 1756 (C3=O), 1726
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 5 2008