3504
A.G. Nigmatov et al. / Tetrahedron Letters 53 (2012) 3502–3505
Table 2
a
Tertiary amine–thiourea 1 catalyzed reaction of C-nucleophiles 2 with
a
-nitroalkenes 3 in liquid CO2
R1
R2
R1
1 (5 mol%)
R1
2a-e
R1
NO2
R2
+
NO2
liquid CO2
100 bar, r.t.
3a-e
4a-l
Entry
R1
R2
Time (h)
Product
Yieldb,c (%)
eec,d,e (%)
1
2f
3
4
5
2a (CO2Et)
2a (CO2Et)
2a (CO2Et)
2a (CO2Et)
2a (CO2Et)
2b (CO2Me)
3a (Ph)
3a (Ph)
3b (4-ClC6H4)
3c (4-MeOC6H4)
3d (2,4-(MeO)2C6H3)
3a (Ph)
4 (2418a
4
)
4a
4a
4b
4c
4d
4e
59 (8618a
62
)
87 (9318a
87
)
8 (4821a
)
95 (9321a
66 (8921a
36 (7321a
68
)
)
)
81 (9021a
82 (9021a
89 (9121a
87
)
)
)
12 (4821a
12 (7221a
4
)
)
6
8 (918b
4 (621b
)
)
86 (8918b
95 (7821b
83 (7121b
48
)
)
)
88 (8618b
88 (7521b
85 (8621b
87
)
)
)
7
8
9
10
11
12
2b (CO2Me)
2b (CO2Me)
2b (CO2Me)
2b (CO2Me)
2c (CO2iPr)
2d (CN)
3b (4-ClC6H4)
3c (4-MeOC6H4)
3d (2,4-(MeO)2C6H3)
3e (Me2CHCH2)
3a (Ph)
4f
12 (1021b
48
)
4g
4h
4i
4j
4k
60 (4818a
)
55 (8818a
)
82 (8118a
)
g
g
g
12 (4818b
4 (0.2518b
)
)
30 (7018b
81 (8518b
)
)
67 (8818b
80 (2518b
)
)
3a (Ph)
O
24 (2421c
)
4l
65 (8421c
)
76 (8921c
)
2e
13
3a (Ph)
a
b
c
d
e
f
The reactions were carried out with 2 (0.4 mmol), 3 (0.2 mmol), and catalyst 1 (4.1 mg, 0.01 mmol) in a 2 ml autoclave filled with CO2 at 100 bar at rt.
Isolated yield.
Reported data are given in brackets.
Enantiomeric excess was determined by HPLC analysis of compounds 4 using a chiral column.
The absolute configuration was determined by comparing the specific rotations of compounds 4 with literature data.
The reaction was carried out with 2a (2 mmol), 3a (1 mmol), and catalyst 1 (20.5 mg, 0.05 mmol) in a 10 ml autoclave.
Reported data for the reaction of 2a with 3e are given in brackets.
g
6. (a) Marqués-López, E.; Herrera, R. P.; Christmann, M. Nat. Prod. Rep. 2010, 27,
1138; (b) Maltsev, O. V.; Beletskaya, I. P.; Zlotin, S. G. Russ. Chem. Rev. 2011,
1067, 80.
autoclave was filled with CO2 by means of a syringe-press to a total
pressure of 100 bar. After 2–60 h of stirring, the autoclave was
slowly depressurized. The residue was recovered by rinsing with
CH2Cl2 and purified by column chromatography on silica gel
(hexane/Et2O = 5/1 as eluent).
9
7. (a) Durand, J.; Teuma, E.; Gomez, M. C. R. Chimie 2007, 10, 152; (b) Zlotin, S. G.;
Makhova, N. N. Mendeleev Commun. 2010, 20, 63.
8. (a) Gruttadauria, M.; Giacalone, F.; Noto, R. Adv. Synth. Catal. 2009, 351, 33; (b)
Raj, M.; Singh, V. K. Chem. Commun. 2009, 6687.
9. Kerton, F. M. Alternative Solvents for Green Chemistry; RSC Publishing:
Cambridge, 2010. 226.
Acknowledgments
10. Leitner, W. Handbook Of Green Chemistry In Supercritical Solvents; Leitner, W.,
Jessop, P. G., Eds.; Wiley-VCH: Weinheim, 2010; Vol. 4, p 1412.
11. (a) Jessop, P. G.; Ikariya, T.; Noyori, R. Chem. Rev. 1999, 99, 475; (b) Oakes, R. S.;
Clifford, A. A.; Rayner, C. M. J. Chem. Soc., Perkin Trans. 1 2001, 917; (c) Beckman,
E. J. J. Supercrit. Fluids 2004, 28, 121; (d) Leitner, W. Appl. Organomet. Chem.
2000, 14, 809; (e) Jessop, P. G. J. Supercrit. Fluids 2006, 38, 211; (f) Kruse, A.;
Vogel, H. Chem. Eng. Technol. 2008, 31, 23.
The work was supported by the Russian Foundation for Basic
Research (Grant No. 11-03-12163-ofi_m).
Supplementary data
12. (a) Jessop, P. G. In Supercritical Fluid Technology for Drug Product Development;
York, P., Kompella, U. B., Shekunov, B. Y., Eds.; Marcel Dekker: New York, 2004;
pp 461–495; (b) Xiao, J.; Nefkens, S. C. A.; Jessop, P. G.; Ikariya, T.; Noyori, R.
Tetrahedron Lett. 1996, 37, 2813; (c) Lyubimov, S. E.; Kuchurov, I. V.; Davankov,
V. A.; Zlotin, S. G. J. Supercrit. Fluids 2009, 50, 118; (d) Mikami, K.; Matsukawa,
S.; Kayaki, Y.; Ikariya, T. Tetrahedron Lett. 2000, 41, 1931; (e) Kainz, S.; Leitner,
W. Catal. Lett. 1998, 55, 223; (f) Francio, G.; Leitner, W. Chem. Commun. 1999,
1663; (g) Francio, G.; Wittmann, K.; Leitner, W. J. Organomet. Chem. 2001, 621,
130; (h) Rodriguez, L.-I.; Rossell, O.; Seco, M.; Orejon, A.; Masdeu-Bulto, A. M. J.
Organomet. Chem. 2008, 693, 1857.
13. (a) Mesiano, A. J.; Beckman, E. J.; Russell, A. J. Chem. Rev. 1999, 99, 623; (b)
Matsuda, T.; Harada, T.; Nakamura, K. Green Chem. 2004, 6, 440; (c) Lozano, P.
Green Chem. 2010, 12, 555.
14. (a) Yoshida, M.; Hara, N.; Okuyama, S. Chem. Commun. 2000, 151; (b) Smith, C.
J.; Tsang, M. W. S.; Holmes, A. B.; Danheiserd, R. L.; Tester, J. W. Org. Biomol.
Chem. 2005, 3, 3767.
Supplementary data associated with this article can be found, in
References
1. (a)Enantioselective Organocatalysis: Reactions and Experimental Procedures;
Dalko, P. I., Ed.; Wiley-VCH: Weinheim, 2007; p 536; (b) Dondoni, A.; Massi,
A. Angew. Chem., Int. Ed. 2008, 47, 4638; (c) Pellissier, H. Recent Developments in
Asymmetric Organocatalysis; RSC Publishing: Cambridge, 2010. 241; (d) Vicario,
J. L.; Badía, D.; Carillo, L.; Reyes, E. Organocatalytic Enantioselective Conjugate
Addition Reactions. A Powerful Tool for the Stereocontrolled Synthesis of Complex
Molecules; RSC Publishing: Cambridge, 2010. 368.
2. (a) Melchiorre, P.; Marigo, M.; Carlone, A.; Bartoli, G. Angew. Chem., Int. Ed.
2008, 47, 6138; (b) Kano, T.; Maruoka, K. Bull. Chem. Soc. Jpn. 2010, 83, 1421.
3. (a) Mukherjee, S.; Yang, J. W.; Hoffman, S.; List, B. Chem. Rev. 2007, 107, 5471;
(b) Cheong, P. H.-Y.; Legault, C. Y.; Um, J. M.; Celebi-Ölcüm, N.; Houk, K. N.
Chem. Rev. 2011, 111, 5042.
4. (a) Erkkilä, A.; Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416; (b) Grošelj,
U.; Seebach, D.; Badine, D. M.; Schweizer, W. B.; Beck, A. K.; Krossing, I.; Klose,
P.; Hayashi, Y.; Uchimaru, T. Helv. Chim. Acta 2009, 92, 1225.
15. Parratt, A. J.; Adams, D. J.; Clifford, A. A.; Rayner, C. M. Chem. Commun. 2004,
2720.
16. Rose, P. M.; Clifford, A. A.; Rayner, C. M. Chem. Commun. 2002, 968.
17. (a) Almaßsi, D.; Alonso, D. A.; Nájera, C. Tetrahedron: Asymmetry 2007, 18, 299;
(b) Roca-Lopez, D.; Sadaba, D.; Delso, I.; Herrera, R. P.; Tejero, T.; Merino, P. .
Tetrahedron: Asymmetry 2010, 21, 2561.
18. (a) Okino, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc. 2003, 125, 12672; (b)
Okino, T.; Hoashi, Y.; Furukawa, T.; Xu, X.; Takemoto, Y. J. Am. Chem. Soc. 2005,
127, 119; (c) Miyabe, H.; Takemoto, Y. Bull. Chem. Soc. Jpn. 2008, 81, 785; (d)
Takemoto, Y. Chem. Pharm. Bull. 2010, 58, 593; (e) Lalonde, M. P.; Chen, Y.;
Jacobsen, E. N. Angew. Chem., Int. Ed. 2006, 45, 6366.
5. (a) Jiang, L.; Zheng, H.-T.; Liu, T.-Y.; Yuea, L.; Chen, Y.-C. Tetrahedron 2007, 63,
5123; (b) Doyle, A. G.; Jacobsen, E. N. Chem. Rev. 2007, 107, 5713; (c) Marcelli,
T.; Hiemstra, H. Synthesis 2010, 1229.