Dual 1,3-dipolar cycloaddition of carbon dioxide: Two CO bonds of CO 2 react in one reaction

Article abstract of DOI:10.1039/c3cc38526d

The first investigation into two CO bonds of CO₂ reacting in one reaction through dual 1,3-dipolar cycloaddition of CO₂ with isocyanides and dialkyl acetylenedicarboxylates has been reported. The reaction proceeded efficiently at 80 °C at a pressure of 1 atm of CO₂, affording symmetric 1,6-dioxospiro[4,4]nonane-3,8-diene derivatives in moderate yields.

Full text of DOI:10.1039/c3cc38526d

ChemComm
View Article Online
View Journal | View Issue
COMMUNICATION
Dual 1,3-dipolar cycloaddition of carbon dioxide:
Q
two C O bonds of CO2 react in one reaction†
Cite this: Chem. Commun., 2013,
49, 2569
Li-Li Zhao, Shun-Yi Wang,* Xiao-Ping Xu and Shun-Jun Ji*
Received 27th November 2012,
Accepted 16th January 2013
DOI: 10.1039/c3cc38526d
www.rsc.org/chemcomm
Q
The first investigation into two C O bonds of CO2 reacting in one
reaction through dual 1,3-dipolar cycloaddition of CO2 with iso-
cyanides and dialkyl acetylenedicarboxylates has been reported.
The reaction proceeded efficiently at 80 8C at a pressure of 1 atm of
CO2, affording symmetric 1,6-dioxospiro[4,4]nonane-3,8-diene
derivatives in moderate yields.
Carbon dioxide (CO2) has attracted much attention1–4 because
of its potential greenhouse effect as a result of its steadily
increasing concentrations in the atmosphere, and because it is
attractive as an abundant, economical, non-toxic, popular
chemical reagent, and is a natural renewable C1 source.5–7 It
is widely accepted that CO2 is so thermodynamically and
kinetically stable that it is considered to be an inert material.
In all reported reactions, only one CQO bond of CO2 is
involved. The other CQO bond remains as a carbonyl group,
and shows different reactivity to that of the original CQO bond
of CO2.8–12 The effective conversion of CO2 via its reactions
with new active intermediates, to expand the scope of CO2
applications, is therefore a hot research topic in organic
chemistry. Reactions involving CO2 can be categorized as
following one of three patterns: (1) formation of a carboxyl
group through nucleophilic attack (pattern a); (2) generation of
a five-membered metallalactone through oxidative cycloaddition
(pattern b);8 and (3) reductive coupling of CO2 to [O2CCO2]2À
(pattern c).13,14 To the best of our knowledge, it has never been
reported that both CQO bonds of CO2 react in one reaction
(Fig. 1). Herein, we report the first example of two CQO bonds
of CO2 reacting in one reaction via a facile dual 1,3-dipolar
cycloaddition of CO2 with isocyanides and dialkyl acetylene-
dicarboxylates.‡ The reaction proceeded efficiently at 80 1C at a
Fig. 1 Scope of typical transformations of CO2.
pressure of 1 atm of CO2, affording symmetric 1,6-dioxospiro-
[4,4]nonane-3,8-diene derivatives in moderate yields.
Isocyanides are indispensable building blocks in modern
organic chemistry.15–19 It has been documented that isocyanides
attack dialkyl acetylenedicarboxylates to give zwitterionic
species, which act as pivotal intermediates. These reactive
zwitterions are readily trapped by carbon electrophiles20 such
as aldehydes,21 ketones,22 esters,23 and sulfonylimines.24 We
hypothesized that it would be interesting to investigate the
reaction of CO2 with zwitterionic species as powerful active
intermediates (Fig. 2). We initiated the study by the reactions of
CO2 with neat isocyanides and dialkyl acetylenedicarboxylates.
To our surprise, the dual 1,3-dipolar cycloaddition product,
1,6-dioxospiro[4,4]nonane-3,8-diene 4a, was obtained in 20%
yield instead of the mono 1,3-dipolar cycloaddition product 3a.
In order to increase the yield of 4a and better understand this
reaction, several reaction conditions, such as different solvents,25
reaction temperatures, and substrate ratios, were screened.
It was found that the optimal reaction conditions were CO2
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
China. E-mail: shunyi@suda.edu.cn, shunjun@suda.edu.cn;
Fax: +86-512-65880307; Tel: +86-512-65880307
† Electronic supplementary information (ESI) available. CCDC 894399. For ESI
and crystallographic data in CIF or other electronic format see DOI: 10.1039/
c3cc38526d
Fig. 2 Attempted dual 1,3-dipolar cycloaddition of CO2 with isocyanide and
DMAD.
c
This journal is The Royal Society of Chemistry 2013
Chem. Commun., 2013, 49, 2569--2571 2569

View Article Online
Communication
ChemComm
(balloon, 1 atm), isocyanide (1a, 1.0 equiv.), and dimethyl
acetylenedicarboxylate (DMAD) (2a, 1.5 equiv.) in toluene at
80 1C. The isolated yield of the desired product increased to
55%. In all these reactions, we also tried to isolate and prove
the existence of compound 3a, but failed.
With the optimal conditions in hand, other isocyanides such
as 2,6-dimethylphenyl isocyanide, benzyl isocyanide, tert-butyl
isocyanide, and n-butyl isocyanide were evaluated for this
reaction. The results are summarized in Table 1. The desired
dual cycloaddition products 4b–4e could be obtained in mode-
rate yields. Isocyanides bearing cyclic aliphatic (4a), aryl (4b),
branched (4d), and linear (4e) groups performed well under the
established reaction conditions. Attempts were made to carry
out similar transformations using methyl 2-isocyanoacetate
(1f), 1-(isocyanomethylsulfonyl)-4-methylbenzene (1g), and
1-[cyclohexylidene(isocyano)methylsulfonyl]-4-methylbenzene (1h)
instead of cyclohexyl isonitrile (1a). However, all failed to
generate the corresponding 1,6-dioxospiro[4,4]nonane-3,8-
diene derivatives under the identical reaction conditions
(Table 1, 4f–4h).26 We then investigated a number of conju-
gated triple bond acceptors. When the conjugated acceptor
Fig. 3 Crystal structure of compound 4i.
diethyl but-2-ynedioate was used, the desired 3,4,8,9-tetra-
substituted 1,6-dioxaspiro[4.4]nona-3,8-diene derivatives (4i–4m)
were isolated in 35–60% yields (Table 1). The structure of
product 4i was further confirmed by single-crystal X-ray analysis
(Fig. 3).§ However, it was found that methyl 2-propynoate,
methyl 3-phenyl-2-propynoate, and diisopropyl but-2-ynedioate
were not suitable for this reaction (Table 1, 4n–4p).
a
Table 1 Dual 1,3-dipolar cycloadditions of CO2
Based on the above results, literature reports27 and in situ IR
experiments,28 we propose a plausible mechanism for this
reaction. It is reasonable to assume that the highly reactive
1 : 1 zwitterionic intermediate A formed by the addition reaction
of isocyanide 1a with dialkyl acetylenedicarboxylate 2a adds to
the carbonyl groups of CO2; one CQO bond of CO2 is broken,
and the resulting species 3a is attacked by another zwitterionic
intermediate A, which then affords the dual 1,3-dipolar cyclo-
addition product 1,6-dioxospiro[4,4]nonane-3,8-diene 4a. When
the concentrations of the reacting species increase, the isocyanide
undergoes addition reaction with two DMAD molecules, giving
the 1,5-zwitterionic intermediate 5a. The 1,5-dipolar inter-
mediate 5a receives electron density from another isocyanide
molecule, and the resulting species 6a is then protonated by
a
Reaction conditions: isocyanide (1, 1.0 mmol), 2 (1.5 mmol), toluene
(2.5 mL), CO2 (balloon, 1 atm); isolated yields.
Fig. 4 Plausible mechanism.
c
2570 Chem. Commun., 2013, 49, 2569--2571
This journal is The Royal Society of Chemistry 2013

View Article Online
ChemComm
Communication
K. Domen, D. L. DuBois, J. Eckert, E. Fujita, D. H. Gibson,
W. A. Goddard, D. W. Goodman, J. Keller, G. J. Kubas,
H. H. Kung, J. E. Lyons, L. E. Manzer, T. J. Marks, K. Morokuma,
K. M. Nicholas, R. Periana, L. Que, J. Rostrup-Nielson, W. M. H.
Sachtler, L. D. Schmidt, A. Sen, G. A. Somorjai, P. C. Stair,
B. R. Stults and W. Tumas, Chem. Rev., 2001, 101, 953.
6 N. Eghbali and C.-J. Li, Green Chem., 2007, 9, 213.
7 J. Louie, Curr. Org. Chem., 2005, 9, 605.
8 T. Sakakura, J.-C. Choi and H. Yasuda, Chem. Rev., 2007, 107, 2365.
9 D. J. Darensbourg, Chem. Rev., 2007, 107, 2388.
H2O to give the hydrolysis product 7a as a side-product. Under
the optimized conditions, 5a and 7a are obtained in yields
of less than 4%, respectively, which proves the existence of the
1,5-dipolar intermediate 5a (Fig. 4).
In conclusion, we have first reported that two CQO bonds of
CO2 react in one reaction through a facile dual 1,3-dipolar
cycloaddition of CO2 with isocyanides and dialkyl acetylenedi-
carboxylates, which afforded the symmetric spiro compounds
1,6-dioxospiro[4,4]nonane-3,8-diene derivatives in moderate
10 J. Ma, J. L. Song, H. Z. Liu, J. L. Liu, Z. F. Zhang, T. Jiang, H. L. Fan
and B. X. Han, Green Chem., 2012, 14, 1743.
yields. It provided a new method for construction of spiro 11 D. H. Gibson, Chem. Rev., 1996, 96, 2063.
12 (a) D. B. Dell’Amico, F. Calderazzo, L. Labella, F. Marchetti and
compounds using CO2. This reaction would attract consider-
able attention in the chemistry of CO2 and inspire new organic
reactions of CO2. Further studies to understand the reaction
mechanism and develop new synthetic methodologies utilizing
CO2 are ongoing in our laboratory.
We gratefully acknowledge the Natural Science Foundation
of China (no. 21042007, 21172162), the Young National Natural
Science Foundation of China (no. 21202111), the Young Natural
Science Foundation of Jiangsu Province (BK2012174), PAPD,
and Soochow University for financial support.
G. Pampaloni, Chem. Rev., 2003, 103, 3857; (b) Z. Han, L. Rong,
J. Wu, L. Zhang, Z. Wang and K. Ding, Angew. Chem., Int. Ed., 2012,
51, 13041; (c) K. J. P. Schouten, Y. Kwon, C. J. M. van der Ham, Z. Qin
and M. T. M. Koper, Chem. Sci., 2011, 2, 1902; (d) E. E. Benson,
C. P. Kubiak, A. J. Sathrum and J. M. Smieja, Chem. Soc. Rev., 2009,
38, 89; (e) Q. Gao, X.-C. Tan, Y.-M. Pan, H.-S. Wang and Y. Liang,
Chem. Commun., 2012, 48, 12080.
13 R. Angamuthu, P. Byers, M. Lutz, A. L. Spek and E. Bouwman,
Science, 2010, 327, 313.
14 W. J. Evans, S. E. Lorenz and J. W. Ziller, Inorg. Chem., 2009,
48, 2001.
¨
15 A. Domling, Chem. Rev., 2006, 106, 17.
16 F. Millich, Chem. Rev., 1972, 72, 101.
¨
17 A. Domling and I. Ugi, Angew. Chem., Int. Ed., 2000, 39, 3168.
Notes and references
18 A. V. Gulevich, A. G. Zhdanko, R. V. A. Orru and V. G. Nenajdenko,
Chem. Rev., 2010, 110, 5235.
19 (a) S. Sadjadi and M. M. Heravi, Tetrahedron, 2011, 67, 2707;
(b) F. De Moliner, L. Banfi, R. Riva and A. Basso, Comb. Chem. High
Throughput Screening, 2011, 14, 782.
20 V. Nair, A. U. Vinoda, N. Abhilasha, R. S. Menona, V. Santhia,
R. L. Varmaa, S. Vijia, S. Mathewa and R. Srinivasb, Tetrahedron,
2003, 59, 10279.
21 (a) V. Nair and A. U. Vinoda, Chem. Commun., 2000, 1019;
(b) R. Ghadari, F. Hajishaabanha, M. Mahyari, A. Shaabani and
H. R. Khavasi, Tetrahedron Lett., 2012, 53, 4018.
22 A. A. Esmaeili and M. Darbanian, Tetrahedron, 2003, 59, 5545.
23 A. Shaabani, A. H. Rezayan, S. Ghasemi and A. A. Sarvary, Tetra-
hedron Lett., 2009, 50, 1456.
24 I. Yavari and H. Djahaniani, Tetrahedron Lett., 2005, 46, 7491.
25 (a) J. M. Zhang, J. Sun, X. C. Zhang, Y. S. Zhao and S. J. Zhang,
‡ General procedure for dual 1,3-dipolar cycloaddition of CO2: isocyanide
1 (1.0 mmol), dialkyl acetylenedicarboxylate 2 (1.5 mmol), and CO2
(balloon, 1 atm) were mixed in 2.5 mL of toluene at 80 1C. The mixture
was stirred at room temperature for 24–48 h. After completion of the
reaction (monitored by TLC), the solvent was removed under reduced
pressure and the residue was separated by column chromatography
(silica gel, Merck 300–400 mesh) using petroleum ether–acetone
(30–15 : 1) as the eluent to afford the desired product 4.
§ Crystal data for 4i, CCDC 894399. C31H42N2O10, Mr = 602.67, mono-
clinic, a = 38.03(2) Å, b = 8.049(3) Å, c = 25.145(11) Å, U = 6625(5) Å3, T =
223(2) K, space group C2/c, Z = 8, 6094 reflections measured, 4120
unique (Rint = 0.0496) which were used in all calculations. The final
wR(F2) was 0.1757 (all data).
1 D. P. Schrag, Science, 2007, 315, 812.
´
Greenhouse Gases: Sci. Technol., 2011, 1, 142; (b) M. Olivares-Marın
and M. M. Maroto-Valer, Greenhouse Gases: Sci. Technol., 2012,
2, 20.
2 H. Li, P. H. Opgenorth, D. G. Wernick, S. Rogers, T.-Y. Wu,
W. Higashide, P. Malati, Y.-X. Huo, K. M. Cho and J. C. Liao, Science,
2012, 335, 1596.
26 (a) M. Adib, B. Mohammadi, E. Sheikhi and H. R. Bijanzadeh, Chin.
Chem. Lett., 2011, 22, 314; (b) S. Kamijo, C. Kanazawa and
Y. Yamamoto, Tetrahedron Lett., 2005, 46, 2563.
27 (a) M. Bayat, H. Imanieh and H. Abbasi, Helv. Chim. Acta, 2010,
93, 753; (b) A. Shaabani, A. H. Rezayan, S. Ghasemi and A. Sarvary,
Tetrahedron Lett., 2009, 50, 1456.
3 J. Agarwal, E. Fujita, H. F. Schaefer and J. T. Muckerman, J. Am.
Chem. Soc., 2012, 134, 5180.
4 S. Horike, K. Kishida, Y. Watanabe, Y. Inubushi, D. Umeyama,
M. Sugimoto, T. Fukushima, M. Inukai and S. Kitagawa, J. Am.
Chem. Soc., 2012, 134, 9852.
5 H. Arakawa, M. Aresta, J. N. Armor, M. A. Barteau, E. J. Bell,
A. T. Beckman, J. E. Bercaw, C. Creutz, E. Dinjus, D. A. Dixon, 28 For details, see ESI†.
c
This journal is The Royal Society of Chemistry 2013
Chem. Commun., 2013, 49, 2569--2571 2571