ZnO-nanoparticles as an efficient catalyst for the synthesis of tetrasubstituted cyclopentadienones using sulfonoketenimides and enaminoesters

Article abstract of DOI:10.1080/10426507.2017.1370593

A convenient and efficient approach to the synthesis of substituted cyclopentadienes is reported based on the reaction of sulfonoketenimides and enaminoesters in good yield. In these reactions, sulfonoketenimides is produced from the reaction of terminal

Full text of DOI:10.1080/10426507.2017.1370593

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
ZnO-nanoparticles as an efficient catalyst for the
synthesis of tetrasubstituted cyclopentadienones
using sulfonoketenimides and enaminoesters
Ali Varasteh Moradi
To cite this article: Ali Varasteh Moradi (2017): ZnO-nanoparticles as an efficient catalyst for the
synthesis of tetrasubstituted cyclopentadienones using sulfonoketenimides and enaminoesters,
Phosphorus, Sulfur, and Silicon and the Related Elements, DOI: 10.1080/10426507.2017.1370593
To link to this article: http://dx.doi.org/10.1080/10426507.2017.1370593
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ACCEPTED MANUSCRIPT
ZnO-nanoparticles as an efficient catalyst for the synthesis of tetrasubstituted
cyclopentadienones using sulfonoketenimides and enaminoesters
Ali Varasteh Moradi*
aDepartment of Chemistry, Gorgan Branch, Islamic Azad University, Gorgan, Iran
Email: avmoradi@yahoo.com
Abstract
A convenient and efficient approach to the synthesis of substituted cyclopentadienes is reported
based on the reaction of sulfonoketenimides and enaminoesters in good yield. In these reactions,
sulfonoketenimides is produced from the reaction of terminal alkynes and sulfonyl azides in the
presence of copper iodide and enaminoesters is prepared via the reaction of dialkyl
acetylenedicarboxylates and primary amines in the presence of ZnO-nanoparticles.
H
C O 2 R''
C u I (1 0 m o l% )
R'O 2 S N
C O 2 R''
Z n O -N P s (1 0 m o l% )
O
O
R''' N H 2
+
+
R
S
+
C H 3 C N , r.t.
R'
N 3
N R'''
H
R
C O 2 R''
O
Keywords
ZnO-nanoparticles; Dialkyl acetylenedicarboxylates; Primary amines; sulfonoketenimides.
1
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Introduction
Multicomponent reactions (MCR) are interesting due to their potential for high synthetic
efficiency and production of complex organic compounds [1-7]. The cyclopentadiene ring
system has enjoyed significant research attention for more than half a century in organic
chemistry and the other research fields [8-15]. Cyclopentadiene is a important diene that is
employed in Diels–Alder reactions. Therefore, the expansion of efficient synthetic methods to
producing of cyclopentadienes has been of interest [16-18]. As well, cyclopentadienes are as
forerunners for the creation of transition-metal complexes in coordination chemistry [19]. Also,
among the various procedures that produce ketenimines, the copper-catalyzed azide-alkyne
cycloaddition reaction has been previously documented [20-22]. Ketenimine intermediates
generated through these could be trapped by diverse nucleophiles [23-28]. In this paper, we show
an efficient synthesis of eneidacyepolcyc derivatives ‎in good yield via the reaction of
sulfonoketenimides 6 that is produced from the reaction of terminal alkynes 1 and sulfonyl
azides 2 in the presence of catalytic amount of copper iodide with intermediate 7 that is
generated from the reaction of dialkyl acetylenedicarboxylate 3 and primary amines 4 in the
presence of ZnO-NPs [29] (Scheme 1).
Result and discussion
In these reactions, the first step is optimization of reaction conditions for achieving to best
conditions for producing of cyclopentadine derivatives 8 (Scheme 1). The conditions of the
reaction involving solvent and catalyst were optimized. For the generation of intermediate 6,
several catalysts such as CuI, CuBr, CuCl and copper powder were tested. Among them CuI give
the best results. Also, several solvents such as CH3CN, DMF, H2O, toluene, diethyl ether and
2
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solvent-free conditions were employed with CH3CN as the best solvent. For preparation of
compound 8, ZnO-nanoparticles, CM-ZnO, pyridine, piperidine, CuO-NPs and TiO2-NPs were
tested as catalysts. Among them, ZnO-NPs are the best catalyst (Table 1).
Under the optimized conditions described above, cyclopentadiene derivatives 8 are generated in
good yields with the amount of ZnO-NPs given as 10 mol%. Using an amount greater than
10mol% does not improve the yield of reactions. The ZnO-NPs that is used in these reactions can
be reused five times without considerable loss of activity. The catalyst was filtered after each
reaction and washed completely with ethyl acetate. Then, it was dried at room temperature for 24
h and used for the next catalytic cycle. ZnO-nanoparticles were prepared according to literature
and SEM and XRD image are confirmed the structure of nanoparticles [28]. The structures of
compounds 8a-h were assigned by IR, 1H NMR, 13C NMR and mass spectral data. For example,
1
in the H NMR spectrum of 8a showed one singlet for methyl protons at (δ 2.36 ppm), one
singlet at (δ3.45 ppm) for NMe protons and one singlet for methoxy proton at (δ3.75 ppm). Also,
two singlets were seen at 7.45 and 8.58 ppm for NH protons along with signals for aromatic
moiety. The 13C NMR spectrum of 8a showed two signals for carbonyl group at 161.5 and 189.7
ppm in agreement with the proposed structure. In addition the mass spectrum of 8a displays the
molecular ion peak for the appropriate m/z values. A proposed mechanism for the producing of
compound 8 is shown in Scheme 2 [23-28]. Enaminone 7 as a nucleophile, is generated from the
initial addition of dialkyl acetylenedicarboxylate 3 to primary amines 4 [28]. Also, the copper
acetylide 9 that is formed from terminal alkyne 1 and CuI is converted to ketenimine 6 after the
reaction with sulfonyl azides 2 by confirmed transformations [23-28]. Ketenimine 6 were reacted
with intermediate 7 in the presence of ZnO-NPs to generate intermediate 12 that is finally
3
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converted to product 8 by intramolecular cyclization and imine-enamine tautomerization
(Scheme 2) [23-28].
Conclusion
Sulfonoketenimides generated from the reaction of terminal alkynes and sulfonyl azides react
with an intermediate that is generated from the reaction of dialkyl acetylenedicarboxylate and
primary amines in the presence of ZnO-NPs (10 mol%) to produce cyclopentadiene derivatives
in good yields.
Experimental
All chemicals employed in this work were prepared from Fluka (Buchs, Switzerland) and were
performed without additional purification. Nanoparticles of ZnO were synthesized according to
the literature report [29]. The morphology of nanostructure of ZnO was determined by scanning
electron microscopy (SEM). X-ray diffraction (XRD) analysis was performed at room
temperature using a Holland Philips Xpert X-ray powder diffractometer with Cu Ka radiation
(λ=0.15406 nm), over the 2θ collection range of 20–80° [29]. Melting points were measured on
an Electrothermal 9100 apparatus. Elemental analyses for C, H, and N were performed using a
Heraeus CHN–O-Rapid analyzer. Mass spectra were recorded on a FINNIGAN-MAT 8430
spectrometer operating at an ionization potential of 70 eV. IR spectra were measured on a
1
Shimadzu IR-460 spectrometer. H, and 13C NMR spectra were measured with a BRUKER
1
13
DRX-500 AVANCE spectrometer at 500.1 and 125.8 MHz, respectively. H, and C, spectra
were obtained for solutions in CDCl3 using TMS as internal standard or 85% H3PO4 as external
standard. The Supplemental Materials contains sample characterization data for the products 8,
and the known catalyst (Figures S 1 – S 8).
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General procedure for preparation of compounds 8
In one pot, to a mixture of sulfonyl azide 2 (1.2 mmol), alkyne 1 (1 mmol) and CuI (0.1 mmol)
was added Et3N (2 mmol) in CH3CN (5 mL). In another pot, to a mixture of dialkyl
acetylenedicarboxylate 3 (1 mmol) and primary amines 4 (1 mmol) in CH3CN (5 mL) was added
ZnO-NPs (10 mol%) at room temperature after 20 min. After 10 min, the sulfonoketenimides
that was synthesized in the first pot was added to the second pot. After completion of reaction (1
h, monitored by TLC), the catalyst was removed by filtration. The solvent was evaporated from
the mixture and residue was purified by column chromatography (4:1 hexane/EtOAc) to afford
products , 8.
Methyl
2-(methylamino)-5-{[(4-methylphenyl)
sulfonyl]amino}-3-oxo-4-phenyl-1,4-
cyclopentadiene-1-carboxylate (8a)
o
Pale yellow powders, m.p. 127-129 C; yield: 0.77 g (94%). IR (KBr) (γmax/cm-1): 1735, 1692,
1595, 1487, 1378, 1285, 1129 cm-1. 1H NMR (500 MHz, CDCl3): δ = 2.36 (3 H, s, Me), 3.45 (3
H, s, NMe), 3.75 (3 H, s, MeO), 7.36 (1 H, t, 3J = 7.5 Hz, CH), 7.42 (2 H, d, 3J = 7.6 Hz, 2 CH),
7.45 (1 H, s, NH), 7.62 (2 H, t, 3J = 7.5 Hz, 2 CH), 7.72 (2 H, d, 3J = 7.6 Hz, 2 CH), 7.83 (2 H, d,
13
3J = 7.6 Hz, 2 CH), 8.58 (1 H, s, NH) ppm. C NMR (125 MHz, CDCl3): δ = 21.5 (CH3), 38.4
(NCH3), 51.6 (MeO), 120.6 (C), 120.8 (C), 125.8 (2CH), 126.4 (2 CH), 127.2 (2 CH), 128.4
(CH), 130.7 (2 CH), 134.2 (C), 137.6 (C), 141.3 (C), 142.5 (C), 143.4 (C), 161.5 (C=O), 189.7
(C=O) ppm. MS (EI, 70 eV): m/z (%) = 412 (M+, 15), 381 (86), 77 (46), 31 (100). Anal.Calcd
for C21H20N2O5S (412.46): C, 61.15; H, 4.89; N, 6.79. Found: C, 61.26; H, 4.98; N, 6.92.
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Methyl 2-(ethylamino)- 3-oxo-5-[(phenylsulfonyl)amino]-4-propyl-1,4-
cyclopentadiene-1-carboxylate (8b)
o
Yellow powders, m.p. 138-140 C; yield: 0.69g (92%). IR (KBr) (γmax/cm-1): 1737, 1694, 1587,
1
3
1488, 1382, 1292, 1134 cm-1. H NMR (500 MHz, CDCl3): δ = 0.96 (3 H, t, J = 7.3 Hz, Me),
1.28 (3 H, t, 3J = 7.3 Hz, Me), 1.54-1.59 (2 H, m, CH2), 1.98 (2 H, t, 3J = 7.3 Hz, CH2), 3.27 (2
3
3
H, t, J = 7.3 Hz, Me), 3.78 (3 H, s, MeO), 7.46 (2 H, t, J = 7.6 Hz, 2 CH), 7.48 (1 H, s, NH),
7.56 (1 H, t, 3J = 7.5 Hz, CH), 7.78 (2 H, d, 3J = 7.6 Hz, 2 CH), 8.28 (1 H, s, NH) ppm. 13C NMR
(125 MHz, CDCl3): δ = 14.6 (CH3), 15.7 (Me), 22.8 (CH2), 31.6 (CH2), 38.2 (CH2), 52.3 (MeO),
119.3 (C), 123.4 (C), 125.2 (2 CH), 128.6 (2 CH), 134.5 (CH), 143.2 (C), 144.6 (C), 145.4 (C),
162.6 (C=O), 190.4 (C=O) ppm. MS (EI, 70 eV): m/z (%) = 378 (M+, 20), 347 (82), 77 (58), 31
(100). Anal.Calcd for C18H22N2O5S (378.44): C, 57.13; H, 5.86; N, 7.40. Found: C, 57.26; H,
5.96; N, 7.54.
Methyl 2-(butylamino)- 3-oxo-5-[(methylsulfonyl) amino]-4-butyl-1,4-
cyclopentadiene-1-carboxylate (8c)
o
Pale yellow powders, m.p. 127-129 C; yield: 0.64g (89%). IR (KBr) (γmax/cm-1): 1739, 1692,
1
3
1584, 1476, 1385, 1293, 1142 cm-1. H NMR (500 MHz, CDCl3): δ = 0.92 (3 H, t, J = 7.3 Hz,
Me), 1.14 (3 H, t, 3J = 7.3 Hz, Me), 1.36-1.42 (4 H, m, 2 CH2), 1.48-1.56 (4 H, m, 2 CH2), 2.75
(2 H, t, 3J = 7.3 Hz, CH2), 3.25 (2 H, t, 3J = 7.3 Hz, Me), 3.32 (3 H, s, Me), 3.78 (3 H, s, MeO),
13
7.52 (1 H, s, NH), 8.14 (1 H, s, NH) ppm. C NMR (125 MHz, CDCl3): δ = 13.2 (CH3), 14.4
(Me), 21.3 (CH2), 22.8 (CH2), 29.5 (2 CH2), 30.2 (CH2), 41.2 (CH3), 43.6 (CH2), 51.8 (MeO),
118.6 (C), 119.7 (C), 140.2 (C), 144.2 (C), 162.4 (C=O), 191.2 (C=O) ppm. MS (EI, 70 eV): m/z
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(%) = 358 (M+, 15), 327 (76), 31 (100). Anal.Calcd for C16H26N2O5S (358.45): C, 53.61; H,
7.31; N, 7.82. Found: C, 53.76; H, 7.45; N, 7.96.
Ethyl 2-(propylamino)- 3-oxo-5-[(methylsulfonyl)amino]-4-propyl-1,4-cyclopentadiene-1-
carboxylate (8d)
o
Pale yellow powders, m.p. 126-128 C; yield: 0.62g (90%). IR (KBr) (γmax/cm-1): 1736, 1687,
1
3
1587, 1477, 1387, 1295, 1146 cm-1. H NMR (500 MHz, CDCl3): δ = 0.95 (3 H, t, J = 7.3 Hz,
Me), 1.06 (3 H, t, 3J = 7.3 Hz, Me), 1.28 (3 H, t, 3J = 7.4 Hz, Me), 1.46-1.53 (2 H, m, CH2), 1.59-
1.68 (2 H, m, CH2), 2.63 (2 H, t, 3J = 7.4 Hz, CH2), 3.18 (2 H, t, 3J = 7.4 Hz, Me), 3.34 (3 H, s,
Me), 4.24 (2 H, q, 3J = 7.4 Hz, CH2O), 7.48 (1 H, s, NH), 8.16 (1 H, s, NH) ppm. 13C NMR (125
MHz, CDCl3): δ = 11.2 (CH3), 14.0 (Me), 14.6 (Me), 23.2 (CH2), 24.3 (CH2), 31.5 (CH2), 41.6
(CH3), 45.8 (CH2), 62.4 (CH2O), 118.8 (C), 122.3 (C), 143.6 (C), 144.8 (C), 162.5 (C=O), 192.4
(C=O) ppm. MS (EI, 70 eV): m/z (%) = 344 (M+, 15), 299 (68), 45 (100). Anal.Calcd for
C15H24N2O5S (344.43): C, 52.31; H, 7.02; N, 8.13. Found: C, 52.44; H, 7.18; N, 8.28.
Methyl
2-(benzylamino)-3-oxo-5-{[(4-methylphenyl)sulfonyl]amino}-4-butyl-1,4-
cyclopentadiene-1-carboxylate (8e)
Yellow powders, m.p. 148-150 oC; yield: 0.87 g (93%). IR (KBr) (γmax/cm-1): 1742, 1698, 1596,
1
3
1492, 1383, 1287, 1135 cm-1. H NMR (500 MHz, CDCl3): δ = 1.12 (3 H, t, J = 7.4 Hz, Me),
3
1.37-1.46 (2 H, m, CH2), 1.52-1.63 (2 H, m, CH2), 2.34 (3 H, s, Me), 2.73 (2 H, t, J = 7.4 Hz,
CH2), 3.78 (3 H, s, MeO), 4.52 (2 H, s, NCH2), 7.32 (1 H, t, 3J = 7.4 Hz, CH), 7.38 (2 H, d, 3J =
3
3
7.6 Hz, 2 CH), 7.47 (1 H, s, NH), 7.52 (2 H, d, J = 7.5 Hz, 2 CH), 7.58 (2 H, d, J = 7.6 Hz, 2
CH), 7.72 (2 H, d, 3J = 7.6 Hz, 2 CH), 8.48 (1 H, s, NH) ppm. 13C NMR (125 MHz, CDCl3): δ =
13.6 (CH3), 21.5 (Me), 22.6 (CH2), 28.4 (CH2), 30.2 (CH2), 46.2 (NCH2), 52.3 (MeO), 118.6 (C),
7
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121.2 (C), 125.7 (2 CH), 126.3 (CH), 127.3 (2 CH), 128.2 (2 CH), 129.4 (2 CH), 137.3 (C),
137.9 (C), 138.6 (C), 142.3 (C), 142.8 (C), 162.3 (C=O), 192.7 (C=O) ppm. MS (EI, 70 eV): m/z
(%) = 468 (M+, 20), 437 (68), 77 (56), 31 (100). Anal.Calcd for C25H28N2O5S (468.57): C, 64.08;
H, 6.02; N, 5.98. Found: C, 64.23; H, 6.18; N, 6.16.
Methyl
2-(4-methoxybenzylamino)-3-oxo-5-[(methylsulfonyl)amino]-4-phenyl-1,4-
cyclopentadiene-1-carboxylate (8f)
o
Pale yellow powders, m.p. 153-155 C; yield: 0.87 g (85%). IR (KBr) (γmax/cm-1): 1739, 1698,
1
1586,1467, 1374, 1293, 1127 cm-1. H NMR (500 MHz, CDCl3): δ = 3.36 (3 H, s, Me), 3.78 (3
H, s, MeO), 3.85 (3 H, s, MeO), 4.53 (2 H, s, NCH2), 7.12 (2 H, d, 3J = 7.6 Hz, 2 CH), 7.28 (2 H,
d, 3J = 7.6 Hz, 2 CH), 7.35 (1 H, t, 3J = 7.5 Hz, CH ), 7.45 (1 H, s, NH), 7.56 (2 H, t, 3J = 7.5 Hz,
2 CH), 7.83 (2 H, d, 3J = 7.6 Hz, 2 CH), 8.53 (1 H, s, NH) ppm. 13C NMR (125 MHz, CDCl3): δ
= 41.2 (CH3), 46.3 (CH2), 51.6 (MeO), 55.6 (MeO), 114.6 (2 CH), 121.3 (C), 121.8 (C), 126.6 (2
CH), 128.4 (CH), 129.5 (2 CH), 130.6 (2 CH), 132.2 (C), 133.8 (C), 141.3 (C), 144.7 (C), 158.6
(C), 162.6 (C=O), 191.8 (C=O) ppm. MS (EI, 70 eV): m/z (%) = 442 (M+, 15), 411 (72), 121
(100), 77 (62), 31 (100). Anal.Calcd for C22H22N2O6S (442.49): C, 59.72; H, 5.01; N, 6.33.
Found: C, 59.87; H, 5.18; N, 6.46.
Methyl
2-(4-methoxybenzylamino)-3-oxo-5-[(methylsulfonyl)amino]-4-butyl-1,4-
cyclopentadiene-1-carboxylate (8g)
o
Yellow powders, m.p. 162-164 C; yield: 0.73 g (87%). IR (KBr) (γmax/cm-1): 1740, 1689,
1
3
1594,1478, 1375, 1286, 1129 cm-1. H NMR (500 MHz, CDCl3): δ = 0.96 (3 H, t, J = 7.4 Hz,
Me), 1.37-1.45 (2 H, m, CH2), 1.48-1.59 (2 H, m, CH2), 2.78 (2 H, t, 3J = 7.3 Hz, CH2), 3.34 (3
H, s, Me), 3.78 (3 H, s, MeO), 3.85 (3 H, s, MeO), 4.52 (2 H, s, NCH2), 7.17 (2 H, d, 3J = 7.8 Hz,
8
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3
13
2 CH), 7.33 (2 H, d, J = 7.8 Hz, 2 CH), 7.48 (1 H, s, NH ), 8.24 (1 H, s, NH) ppm. C NMR
(125 MHz, CDCl3): δ = 13.8 (Me), 22.6 (CH2), 28.7 (CH2), 30.4 (CH2), 41.3 (CH3), 46.5 (CH2),
52.3 (MeO), 55.7 (MeO), 114.5 (2 CH), 118.6 (C), 121.7 (C), 129.6 (2 CH), 132.4 (C), 140.6
(C), 142.3 (C), 159.2 (C), 161.8 (C=O), 192.3 (C=O) ppm. MS (EI, 70 eV): m/z (%) = 422 (M+,
15), 391 (86), 121 (100), 77 (68), 31 (100). Anal.Calcd for C20H26N2O6S (422.49): C, 56.86; H,
6.20; N, 6.63. Found: C, 56.98; H, 6.37; N, 6.78.
Ethyl
2-(4-methylbenzylamino)-3-oxo-5-[(methylsulfonyl)amino]-4-propyl-1,4-
cyclopentadiene-1-carboxylate (8h)
o
Pale yellow powders, m.p. 149-151 C; yield: 0.71 g (87%). IR (KBr) (γmax/cm-1): 1738, 1682,
1
1587,1486, 1378, 1295, 1137 cm-1. H NMR (500 MHz, CDCl3): δ = 0.96 (3 H, t,3J = 7.4 Hz,
Me), 1.24 (3 H, t, 3J = 7.4 Hz, Me), 1.59-1.62 (2 H, m, CH2), 2.34 (3 H, s, CH3), 2.62 (2 H, t, 3J
= 7.4 Hz, CH2), 3.34 (3 H, s, Me), 4.22 (2 H, q, 3J = 7.4 Hz, CH2O), 4.53 (2 H, s, NCH2), 7.23 (2
H, d, 3J = 7.8 Hz, 2 CH), 7.33 (2 H, d, 3J = 7.8 Hz, 2 CH), 7.47 (1 H, s, NH ), 8.26 (1 H, s, NH)
ppm. 13C NMR (125 MHz, CDCl3): δ = 13.2 (Me), 14.3 (Me), 21.2 (Me), 23.4 (CH2), 31.7
(CH2), 41.4 (Me), 46.5 (CH2), 63.4 (CH2O), 120.7 (C), 122.3 (C), 127.4 (2 CH), 128.6 (2 CH),
131.2 (C), 135.8 (C), 142.7 (C), 146.6 (C), 162.5 (C=O), 192.7 (C=O) ppm. MS (EI, 70 eV): m/z
(%) = 406 (M+, 15), 361 (64), 105 (100), 77 (58), 45 (100). Anal.Calcd for C20H26N2O5S
(406.49): C, 59.09; H, 6.45; N, 6.89. Found: C, 59.22; H, 6.63; N, 6.98.
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Table 1. Optimization the reaction condition for formation of 8a.
Entry
Catalyst
Mol % of
Catalyst
none
10 mol%
15 mol%
5 mol%
10 mol%
15 mol%
20 mol%
10 mol%
10 mol%
10 mol%
Yeild
(%)
-----
28
30
85
94
95
87
75
1
2
3
4
5
6
7
8
9
none
CM-ZnO
CM-ZnO
NP-ZnO
NP-ZnO
NP-ZnO
NP-ZnO
KF/CP NPs
CuO NPs
TiO2NPs
58
45
10
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C O 2 R''
R''' N H 2
+
C O 2 R''
3
4
C H 3 C N , r.t., 1 h
R'''
N H
H
H
R
R''O 2
C
O
O
C O 2 R''
R'O 2 S N
S
C O 2 R''
1
C u I (1 0 m o l% )
C H 3 C N , r.t., 6 h
R'
N
C
7
+
Z n O -N P s (1 0 m o l% )
N R'''
H
R
O
O
S
O
R
H
R'
N 3
8
2
6
Y ield % o f 8
R '''
R ''
8
R
R '
a
M e
p -to l
P h
M e
E t
9 4
9 2
n -P r
n -B u
n -P r
b
c
M e
M e
E t
P h
M e
n -B u
8 9
9 0
9 3
M e
n -P r
B n
d
e
p -to l M e
n -B u
M e
M e
M e
M e
M e
E t
P h
4 -M eO -B n
f
8 5
g
n -B u
4 -M eO -B n
4 -M e-B n
8 7
8 7
n -P r
h
Scheme 1 Synthesis of cyclopentadiene derivatives 8
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O
O
S
R
S O 2 R'
R
C u
N 2
R
N
+
H
N
R'
+ 2
1 + C u I
_
C
N 2
N
N
C u
S O 2 R'
N
C u
H
R
6
1 1
9
1 0
R'''
N H
C O 2 R''
H
R''' N H 2
+
R''O 2
C
C O 2 R''
C O 2 R''
7
4
3
O
O
H
S
R'O 2 S N
C O 2 R''
N R'''
R'
R'O 2 S N
C O 2 R''
N
C
H
Z n O -N P s
6
7
+
R
H
C O 2 R''
N R'''
R
_
N R'''
H
R
O
H
O
O
O R''
8
1 3
1 2
Scheme 2. Proposed mechanism for the synthesis of cyclopentadiene 8.
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