Synthesis of cyano-pyrrolo[1,2-a][1,10]phenanthroline derivatives using a multicomponent condensation

Article abstract of DOI:10.1002/jhet.1532

1,10-Phenanthroline reacts with malonitrile and aldehydes in the presence of isocyanides as domino-Knoevenagel-nucleophilic cycloaddition for generation of a new class of 10-(aryl)-11-(alkyl- or arylamino-)pyrrolo[1,2-a][1,10] phenanthroline-9-carbonitrile compounds in excellent yield. All compounds are fully characterized with one structurally authenticated by a single X-ray diffraction study.

Full text of DOI:10.1002/jhet.1532

Month 2013 Synthesis of Cyano-pyrrolo[1,2-a][1,10]phenanthroline Derivatives Using
a Multicomponent Condensation
a
b
b
b
*
Ghasem Marandi, Nourallah Hazeri, Malek T. Maghsoodlou, Sayyed M. Habibi-Khorassani,
Niloufar Akbarzadeh Torbati,b Faramarz Rostami-Charati,c Brian W. Skelton,d and Mohamed Makhad
aShahid Bakeri High Education Center of Miandoab, Urmia University, Urmia, Iran
bDepartment of Chemistry, The University of Sistan and Baluchestan, P. O. Box: 98135-674, Zahedan, Iran
cGonbad Institutes of Higher Education, P.O. Box 163, Gonbad, Iran
dChemistry School of Biomedical, Biomolecular and Chemical Science, M313, University of Western Australia, Perth,
Western Australia 6009, Australia
*
E-mail: mt_maghsoodlou@yahoo.com
Received May 31, 2011
DOI 10.1002/jhet.1532
Published online 00 Month 2013 in Wiley Online Library (wileyonlinelibrary.com).
CN
Z
Y
X
Y
CHO
N
N
NC
NC
CH2Cl2
r.t
+
+
R
+
N C
N
X
Z
N
N
H
R
R: cyclohexyl, 2, 6-dimethylphenyl
X: Cl, H
Y: H, CH3, NO2
Z: H, F
1,10-Phenanthroline reacts with malonitrile and aldehydes in the presence of isocyanides as domino-
Knoevenagel-nucleophilic cycloaddition for generation of a new class of 10-(aryl)-11-(alkyl- or arylamino-)
pyrrolo[1,2-a][1,10]phenanthroline-9-carbonitrile compounds in excellent yield. All compounds are fully
characterized with one structurally authenticated by a single X-ray diffraction study.
J. Heterocyclic Chem., 00, 00 (2013).
INTRODUCTION
2, isocyanides 3, and phenanthroline 4, which lead to com-
pounds 5, in excellent yields, shown in Scheme 1.
Extensive researches revolving around the biological,
medicinal, photographic, and other useful applications of
substituted indolizines have been made, resulting in frequent
reviews of the chemistry, synthesis, and properties of this
system and its analogs [1–5]. The increasing demand for
mild, new, and efficient synthetic methods for indolizine
heterocycles is due to their importance in the fields of biology
and pharmacology [6–13].
Although there are a number of reports regarding new indo-
lizines in recent years [14–20], the present article describes the
synthesis of new indolizines with helical structure. In continu-
ation of our interest in multicomponent reactions [21–23], we
have developed an efficient condensation reaction of four
components involving benzaldehyde derivatives 1, malonitrile
2, and isocyanides 3 in the presence of phenanthroline 4 to ac-
cess unsymmetrical pyrroles [24]. We have established a proof
of concept for such multicomponent condensation to access
this class of compounds. Such an approach could be of interest
to organic chemists in general. We deployed aldehyde with
electron withdrawing groups and two different types of iso-
cyanides bearing cyclohexyl or dimethylphenyl substituents.
Compounds 5 are stable solids whose structures are fully
characterized and supported by elemental analysis and
1
spectroscopic data of FTIR, H NMR and 13C NMR, and
mass spectroscopy. For instance, the mass spectrum of 5a
displayed the molecular ion [M+] signal at m/z = 450 that
is consistent with the product structure. The IR spectrum
of 5a showed absorption at 3421 and 2207 cmÀ1 indicating
the presence of NH and CN functional groups.
The 1H NMR spectrum of 5a exhibited multiplet signals
arising from five methylene protons of the cyclohexyl
group at d = 0.52–1.19 ppm and a multiplet at d = 2.24 ppm
from NCH of the cyclohexyl group.
1
Characteristic signals of NH proton in H NMR spec-
trum of 5a are observed at d = 6.09 ppm as a broad singlet.
The aromatic protons of 5a resonated at d = 7.31–9.10 ppm
in the aromatic region.
The 13C NMR spectrum of compound 5a showed char-
acteristic signals for the carbon containing the cyanide
group at d = 84.2 ppm, whereas the carbon of the cyanide
group resonance appears at d = 116.9 ppm. The detailed
spectroscopic information of compound 5a is available in
the experimental section.
RESULTS AND DISCUSSION
Single-crystal X-ray diffraction [25] was used to authen-
ticate structure of compound 5b. Prismatic dark-red crystal
of 5b was prepared by slow evaporation of a saturated
Herein, we now describe the results of the condensation
reaction between benzaldehyde derivatives 1, malonitrile
© 2013 HeteroCorporation

G. Marandi, N. Hazeri, M. T. Maghsoodlon, S. M. Habibi-Khorassani, N. A. Torbati,
F. Rostami-Charati, B. W. Skelton, and M. Makha
Vol 000
Scheme 1. Synthesis of 10-(aryl)-11-(alkyl- or arylamino-)pyrrolo[1,2-a][1,10]phenanthroline-9-carbonitrile derivatives.
Z
X
CN
8
9
7
Z
10
Y
X
Y
CHO
NC
N
6
5
11
CH2Cl2
r.t
+
+
R
N
+
C
N
R
N1
NC
N
N
3
H
5
1
2
4
2
4
3
R
5
a
Yield%
93
Y
Z
X
cyclohexyl
Cl
H
H
H
H
b
c
2, 6-dimethylphenyl Cl
97
94
cyclohexyl
H
NO2
CH3
H
H
H
F
d
e
cyclohexyl
H
93
96
cyclohexyl
H
solution of dichloromethane. Compound 5b crystallizes in
the triclinic space group, Z = 2, with the asymmetric unit
comprising one molecule, shown in Figure 1.
Proton shift and HCN elimination for aromatization
occur as proposed in the mechanism [26,27] shown in
Scheme 2. Such a mechanism is consistent with the general
structure of compound 5a and is supported by spectro-
scopic data.
the multicomponent reaction involving isocyanides. The
products were obtained in quantitative yield without any
prior activation or modifications. It seems that its ease of
work-up and mild reaction conditions make it a useful
approach to modern synthetic routes.
EXPERIMENTAL
Helical structure and some interesting conformational
parameters such as bond length, bond angels, and torsion
angels of structure 5b are shown in Figure 2.
In conclusion, we believe that the recent method benefits
from a mild, simple, efficient, and one-pot synthetic
procedure for the preparation of substituted phenanthroline
derivatives with the probable pharmaceutical properties in
Melting points and IR spectra of all compounds were measured
on an Electrothermal 9100 apparatus (Mount Holly, NJ) and a
JASCO FTIR spectrometer (Easton, MD), respectively. Also, the
1H NMR and 13C NMR spectra were recorded on a BRUKER
DRX-500 AVANCE instrument (Rheinstetten, Germany) using
CDCl3 as the applied solvent and TMS as internal standard at
500.1 and 125.8 MHz, respectively. Elemental analyses for C, H,
and N were performed using a Heraeus CHN-O-Rapid analyzer
(Banau, Germany). In addition, the mass spectra were recorded on
Shimadzu GCMS-QP5050A mass spectrometer (Kyoto, Japan)
operating at an ionization potential of 70 eV. Phenanthroline, maloni-
trile, isocyanide, and aldehyde derivatives were purchased from
Fluka (Buchs, Switzerland), Merck (Darmstadt, Germany), and
Aldrich (Milwaukee, WI) companies, respectively, and used without
further purification.
General procedure for synthesis of compounds 5 (exemplified
by 5a). To a stirred solution of 3-cholorobenzaldehyde (1 mmol),
malonitrile (1 mmol), and phenanthroline (1 mmol) in CH2Cl2
(10 mL) was added, dropwise, a mixture of cyclohexyl isocyanide
(1.1 mmol) in CH2Cl2 (3 mL) over 5 min at ambient temperature.
The reaction mixture was stirred at ambient temperature for
15–48 h. The solvent was removed under reduced pressure, and the
crude product was washed with diethyl ether (2 Â 3mL) and
recrystallized by slow evaporation method (CH2Cl2/n-Hexane),
then the crystalline solid was dried to afford compound 5a.
10-(3-Chlorophenyl)-11-(cyclohexylamino)pyrrolo[1,2-a]
[1,10]phenanthroline-9-carbonitrile (5a). Red crystals; (0.42 g),
yield 93%; mp 213–216ꢀC, IR (KBr) (nmax, cmÀ1): 3421 (NH),
2207 (CN), 1638 (C═N). MS, m/z (%) = 452 (M+ +2, 33), 451
(M+ +1, 33), 450 (M+, 85), 367 (100), 353 (4), 340 (7), 332 (24),
306 (4), 230 (2), 83 (4), 55 (18), 41 (15). Anal. Calcd for
C28H23ClN4 (450.96): C, 74.57; H, 5.14; N, 12.42. Found:
C, 74.50; H, 4.99; N, 12.51. 1H NMR (500.1 MHz, CDCl3): 0.52–
Figure 1. Molecular structure of the compound 5b. Bonds to the disor-
dered components are shown as dotted lines. The intramolecular H bond
is indicated as a dashed line.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2013
Multicomponent Condensation for Generation of Cyano-pyrrolo[1,2-a][1,10]phenanthroline Derivatives
Scheme 2. Proposed mechanism for synthesis of 10-(aryl)-11-(alkyl- or arylamino-)pyrrolo[1,2-a][1,10]phenanthroline-9-carbonitriles.
Cl
H
CN
C
Cl
H
N
Cl
CHO
CN
NC
C
N
-H2O
+
3a
CN
NC
N
N
NC
1a
2
4
Cl
Cl
H
Cl
N
N
NC
NC
H
N
H
N
H
NC
N
N
N
-HCN
CN
CN
N
N
[1,3] H shift
Cl
H
N
NC
N
N
5a
N19
C19
N21
N11
C22
C12
°
Entry
Entry
Entry
Bond length
Atom1
Atom1
(A)
Atom2
Atom2
Atom3 Angle (°)
Atom3
Atom4 Angle (°)
1
2
3
4
5
N21 C22
C12 C22
N11 C12
N11 C19
C19 N19
1.366(2)
1.439(3)
1.426(2)
1.409(2)
1.370(2)
1
2
3
4
N21
N11
C12
N11
C22
C12
N11
C19
C12
C22
C19
N19
120.8(2)
125.2(1)
132.6(1)
121.9(1)
1
2
N11
C19
C12
N11
C22
C12
N21
-11.6(3)
-20.5(3)
C22
N19
3
C12
N11
C19
-9.2(3)
Figure 2. Selected bond lengths (Å), bond angles (ꢀ), and torsion angles (ꢀ) in helical structure of compound 5b.[Color figure can be viewed in the online
issue, which is available at wileyonlinelibrary.com.]
1.19 (10H, m, 5 CH2 of cyclohexyl), 2.24 (1H, m, NCH of
cyclohexyl), 6.09 (1H, br s, NH), 7.31 (1H, dq, J1 =0.7,
J2 =7.8Hz, CHchlorophen), 7.38 (1H, d, J=9.0Hz, C5-H), 7.39 (1H,
t, J=8.2Hz, CHchlorophen), 7.59 (1H, dd, J1 =4.3, J2 =8.2Hz, C3-
H), 7.79 (1H, d, J=9.0Hz, C6-H), 7.83 (1H, d, J=8.5Hz, C8-H),
7.86 (1H, d, J=8.5Hz, C7-H), 7.93 (1H, dd, J1 =7.8, J2 =8.0Hz,
CHchlorophen), 8.19 (1H, t, J=1.8Hz, CHchlorophen), 8.36 (1H, dd,
J1 =1.8, J2 =8.2Hz, C4-H), 9.10 (1H, dd, J1 =1.8, J2 =4.3Hz, C2-
H). 13C NMR (125.8 MHz, CDCl3): 24.2, 25.5, 33.4 and 56.6
(5 CH2 and HNC of cyclohexyl), 84.2 (C9), 116.9 (-CN), 118.7,
121.0 (2 CHphen), 122.2 and 125.4 (2 CHchlorophen), 127.1
(CHphen), 127.4 (CHchlorophen), 127.5 (CHphen), 128.1 (C10), 129.0,
129.4, 129.6 and 130.1 (2 Cphen and 2 CHphen), 134.1 and 135.4
(2 Cchlorophen), 136.5 (Cphen), 137.1 (CHchlorophen), 137.9 (Cphen),
139.8 (C11), 147.8 and 150.2 (Cphen and CHphen).
10-(3-Chlorophenyl)-11-(2,6-dimethylphenylamino)pyrrolo
[1,2-a][1,10]phenanthroline-9-carbonitrile (5b). Red crystals;
(0.46 g), yield 97%; mp 267–270ꢀC (decomposed), IR (KBr)
(nmax, cmÀ1): 3422 (NH), 2207 (CN), 1664 (C═N). MS, m/z
(%) = 474 (M+ + 2, 7), 473 (M+ +1, 7), 472 (M+, 18), 376 (58),
367 (18), 328 (39), 272 (100), 199 (11), 180 (66). Anal. Calcd for
C30H21ClN4 (472.97): C, 76.18; H, 4.48; N, 11.85. Found:
1
C, 76.24; H, 4.43; N, 11.92. H NMR (500.1 MHz, CDCl3): 1.83
(6H, s, ArMe2), 6.50 (1H, t, J=7.5 Hz, Ar-H), 6.65 (2H,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

G. Marandi, N. Hazeri, M. T. Maghsoodlon, S. M. Habibi-Khorassani, N. A. Torbati,
F. Rostami-Charati, B. W. Skelton, and M. Makha
Vol 000
d, J=7.5Hz, Ar-H), 7.05 (1H, d, J=8.2Hz, CHchlorophen), 7.11 (1H,
t, J=7.9Hz, CHchlorophen), 7.36 (1H, t, J=7.6Hz, C5-H), 7.40 (1H,
br s, C6-H), 7.46 (1H, d, J=8.9Hz, C7-H), 7.61 (1H, dd, J1 =4.2,
J2 =8.1Hz, C3-H), 7.88 (1H, d, J=8.9Hz, C8-H), 7.91 (2H, br s,
2 CHchlorophen), 8.38 (1H, dd, J1 =1.5, J2 =8.1Hz, C4-H), 8.49
(1H, br s, NH), 9.12 (1H, dd, J1 =1.5, J2 =4.2Hz,
C2-H). 13C NMR (125.8 MHz, CDCl3): 18.0 (ArMe2), 83.7 (C9),
116.2 (-CN), 118.3, 120.6 (2 CHphen), 121.4 and 121.8
(2 CHchlorophen), 125.5 (CHaryl), 126.3 and 126.6 (2 CHphen), 127.0
(C10), 127.7 (CHphen), 128.2 (Cphen), 128.3 (2 CHaryl and
CHchlorophen), 128.6 (CHphen), 129.1 (Cphen), 133.1 (2 Caryl), 133.1 and
133.9 (2 Cphen), 136.2 and 137.2 (2 Cchlorophen), 139.4 (C11), 140.2
(Caryl), 147.9 and 150.1 (Cphen and CHphen).
11-(Cyclohexylamino)-10-(4-nitrophenyl)H-pyrrolo[1,2-a]
[1,10]phenanthroline-9-carbonitrile (5c). Pale white crystals;
(0.43 g), yield 94%; mp 236–239ꢀC. IR (KBr) (nmax, cmÀ1): 3213
(NH), 2209 (CN), 1662 (C═N). MS, m/z (%)= 462 (M+ + 1, 14),
461 (M+, 44), 378 (87), 331 (45), 306 (7), 180 (100), 98 (6), 83
(12), 55 (21), 41 (14). Anal. Calcd for C28H23N5O2 (461.51):
C, 72.87; H, 5.02; N, 15.17. Found: C, 72.93; H, 5.07; N, 15.09.
1H NMR (500.1MHz, CDCl3): 0.54–1.24 (10H, m, 5 CH2 of
cyclohexyl), 2.25 (1H, m, NCH of cyclohexyl), 7.46 (1H, d,
J = 8.9 Hz, C5-H), 7.64 (1H, dd, J1 = 4.2, J2 = 7.9 Hz, C3-H), 7.84
(1H, d, J = 8.9 Hz, C6-H), 7.89 (1H, d, J = 8.5 Hz, C7-H), 7.92
(1H, d, J = 8.5 Hz, CHnitrophen), 8.29 (1H, d, J = 8.5 Hz, C8-H),
8.31–8.39 (3H, m, 3 CHnitrophen), 8.42 (1H, dd, J1 = 1.7,
J2 = 7.9 Hz, C4-H), 9.13 (1H, dd, J1 = 1.7, J2 = 4.2 Hz, C2-H), 9.18
(1H, br s, NH). 13C NMR (125.8 MHz, CDCl3): 24.2, 25.4, 33.4
and 57.1 (5 CH2 and HNC of cyclohexyl), 83.8 (C9), 116.8
(-CN), 118.6, 121.2 (2 CHphen), 123.1 (CHphen), 123.7
(2 CHnitrophen), 125.8 (CHphen), 126.2 (Cphen), 127.5 (CHphen), 128.2
(C10), 129.7 (CHphen), 130.1, 136.1 and 137.1 (2 Cphen), 137.4
(2 CHnitrophen), 139.6 (Cnitrophen), 140.7 (C11), 146.4 (Cnitrophen),
147.9 and 150.1 (Cphen and CHphen).
11-(Cyclohexylamino)-10-(p-tolyl)pyrrolo[1,2-a][1,10]
phenanthroline-9-carbonitrile (5d). Red crystals; (0.42 g), yield
93%; mp 167–170ꢀC. IR (KBr) (nmax, cmÀ1): 3373 (NH), 2204
(CN), 1649 (C═N). MS, m/z (%) = 431 (M+ + 1, 6), 430 (M+, 20),
347 (77), 180 (100), 154 (18), 119 (18), 83 (13), 55 (25), 41 (19).
Anal. Calcd for C29H26N4 (430.54): C, 80.90; H, 6.09; N, 13.01.
Found: C, 80.96; H, 5.98; N, 12.93. 1H NMR (500.1 MHz,
CDCl3): 0.55–1.28 (10H, m, 5 CH2 of cyclohexyl), 2.28 (1H,
m, NCH of cyclohexyl), 2.31 (3H, s, CH3), 6.07 (1H, br s, NH),
7.32 (2H, d, J=8.0Hz, 2 CHtolyl), 7.41 (1H, d, J=8.9Hz, C5-H),
7.60 (1H, dd, J1 =4.3, J2 =8.1Hz, C3-H), 7.85 (1H, d, J=8.9Hz,
C6-H), 7.87 (2H, br s, C7-H, C8-H), 7.87 (2H, d, J =8.0Hz, 2
CHtolyl), 8.38 (1H, dd, J1 =1.8, J2 =8.1Hz, C4-H), 9.12 (1H, dd,
J1 =1.8, J2 =4.3Hz, C2-H). 13C NMR (125.8 MHz, CDCl3): 21.2
(CH3), 24.1, 25.4, 33.2 and 56.0 (5 CH2 and HNC of cyclohexyl),
84.4 (C9), 117.2 (-CN), 118.5, 120.7 (2 CHphen), 121.5 and 125.0
(2 CHphen), 127.3 (CHphen), 127.9 (Ctolyl), 128.8 (Cphen), 128.9 and
129.2 (4 CHtolyl), 129.9 (C10), 130.4 (Cphen), 136.2 (Ctolyl), 136.8
(C11), 136.9 (CHphen), 137.2 (Cphen), 139.8 (Cphen), 147.5 and
150.2 (CHphen and Cphen).
NCH of cyclohexyl), 6.18 (1H, br s, NH), 7.26 (1H, t, J=5.8Hz,
CHfluorophen), 7.30 (1H, t, J=7.5Hz, CHfluorophen), 7.40 (1H, m,
CHfluorophen), 7.42 (1H, d, J =8.9Hz, C8-H), 7.63 (1H, dd, J1 =4.2,
J2 =8.1Hz, C3-H), 7.79 (1H, dt, J1 =1.9, J2 =7.9Hz, CHfluorophen),
7.85 (1H, d, J=8.9Hz, C7-H), 7.88 (2H, br s, C5-H and C6-H),
8.38 (1H, dd, J1 =1.5, J2 =8.1Hz, C4-H), 9.10 (1H, dd, J1 =1.5,
J2 =4.2Hz, C2-H). 13C NMR (125.8 MHz, CDCl3): 24.1, 25.4,
33.2 and 55.7 (5 CH2 and HNC of cyclohexyl), 85.9 (C9), 115.8
(d, JCF =13.2Hz, CHfluorophen), 116.0 (-CN), 118.6, 120.7 (2
CHphen), 121.4 (d, JCF =15.1 Hz, Cfluorophen), 122.9 (Cphen), 123.8
(d, JCF =3.4Hz, CHfluorophen), 125.2 (CHphen), 126.4 (Cphen), 127.2
(CHphen), 127.9 (CHphen), 128.8 (C10), 129.3 (d, JCF =7.9Hz,
CHfluorophen), 129.9 (Cphen), 135.9 (d, JCF =6.8Hz, CHfluorophen),
138.1 (Cphen), 138.7 (C11), 138.9 (CHphen), 147.6 and 150.1
(CHphen and Cphen), 160.3 (d, JCF = 248.4 Hz, CHfluorophen).
Crystal refinement details for compound 5b. C30H21ClN4,
M= 472.96, F(000) = 492, triclinic, P1, Z=2, T=100(2)K,
a= 8.1485(6), b= 12.1418(10), c= 12.2529(9) Å, a = 77.113(7),
b = 85.161(6), g = 74.723(7)ꢀ, V = 1139.56(15) Å3; Dc =
1.378 g cmÀ3
;
m
Mo = 0.196 mmÀ1
;
θ
max = 28.7ꢀ; R1 (I > 2s
(I)) = 0.0444, wR2 (all data) = 0.0870, GOF = 0.864; |Δrmax| =
0.31e ÅÀ3. Crystallographic data were collected at 100(2) K on an
Oxford Diffraction Xcalibur diffractometer (Oxford Diffraction,
Oxford, UK) fitted with graphite-monochromated Mo Ka
radiation yielding 9062 reflections, these merging to 5049 unique
after multiscan absorption corrections (Rint = 0.0339), with
2889 reflections having I > 2s(I). The structure was refined
against F2 with full-matrix least-squares using the program
SHELXL-97 [25]. All H atoms were added at calculated positions
and refined by use of a riding model with isotropic displacement
parameters based on that of the parent atom. Anisotropic
displacement parameters were employed throughout for the
nonhydrogen atoms. The Ph ring 18n is rotationally disordered
about the C181-C184 line resulting in the Cl atom being
disordered over the 3-position and 5-position with occupancies
refined to 0.655(1) and its complement for the two sites. The
crystal structure for 5b is depicted in Figure 1 where ellipsoids
have been drawn at the 50% probability level. CCDC number
745666 contains the crystallographic data for compound 5b.
These data can be obtained free of charge at www.ccdc.cam.ac.
uk/conts/retrieving.html or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(internat.) +44-1223/336-033; Email: deposit@ccdc.cam.ac.uk.
Acknowledgments. We gratefully acknowledge the financial
support of the Research Council of the University of Sistan and
Baluchestan.
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11-(Cyclohexylamino)-10-(2-fluorophenyl)pyrrolo[1,2-a][1,10]
phenanthroline-9-carbonitrile (5e). Light red crystals; (0.42 g),
yield 96%; mp 146–149ꢀC. IR (KBr) (nmax, cmÀ1): 3417 (NH),
2204 (CN), 1656 (C═N). MS, m/z (%) = 435 (M+ +1, 9), 434 (M+,
28), 351 (100), 324 (7), 180 (64), 83 (6), 55 (15), 41 (12). Anal.
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CDCl3): 0.55–1.24 (10H, m, 5 CH2 of cyclohexyl), 2.27 (1H, m,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2013
Multicomponent Condensation for Generation of Cyano-pyrrolo[1,2-a][1,10]phenanthroline Derivatives
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet