A Cheap Amino Alcohol Catalyzed One-Pot
Letters in Organic Chemistry, 2010, Vol. 7, No. 1
67
[6]
Hassanien, A. A.; Zahrran, M. A.; El-Gaby, M. S. A.; Ghorab,
M.M. Utility of 2-amino-4,5,6,8-tetrahydro-7H-chromene-3-
carbonitriles in synthesis of chromeno [2,3-d] pyrimidine and
chromeno [3,2-e] [1,2,4] triazolo [1,5-c] pyrimidine derivatives of
pharmaceuticca interest. J. Indian Chem. Soc., 1999, 76, 350.
(a) Zhou, J. F.; Tu, S. J.; Gao, Y.; Ji, M. One pot synthesis of
pyrans and pyrano [2,3-c] pyrazole derivatives under microwave
irradiation. Chin. J. Org. Chem., 2001, 21, 742. (b) Shi, F.; Zhou,
D. X.; Li, C. M.; Shao, Q. Q.; Cao, L. J.; Tu, S. J. An efficient and
facile microwave-assisted synthesis of benzo[b][4,7]phenanthroline
derivatives in water. J. Heterocycl. Chem., 2008, 45, 405. (c) Abd
El-Rahman, N. M.; El-Kateb, A. A.; Mady, M. F. Simplified
approach to the uncatalyzed knoevenagel condensation and michael
addition reactions in water using microwave irradiation. Synth.
Commun., 2007, 37, 3961. (d) Tu, S. J.; Gao, Y.; Guo, C.; Shi, D.
Q.; Lu, Z. S. A convenient synthesis of 2-amino-5,6,7,8-tetrahydro-
5-oxo-4-aryl-7,7-dimethyl-4H-benzo-[b]-pyran-3-carbo-nitrile
under microwave irradiation. Synth. Commun., 2002, 32, 2137.
Tu, S. J.; Jiang, H.; Zhuang, Q. Y.; Miao, C. B.; Shi, D. Q.; Wang,
X. S.; Gao, Y. One-pot synthesis of 2-amino-3-cyano-4-aryl-7,7-
dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-benzo [b] pyran under
ultrasonic irradiation without catalyst. Chin. J. Org. Chem., 2003,
23, 488.
(a) Jiang, Z. Q.; Ji, S. J.; Lu, J.; Yang, J. M. A mild and efficient
synthesis of 5-oxo-5,6,7,8-tetrahydro-4H-benzo-[b]-pyran deriva-
tives in room temperature ionic liquids. Chin. J. Chem., 2005, 23,
1085. (b) Shaabani, A.; Samadi, S.; Badri, Z.; Rahmati, A. Ionic
liquid promoted efficient and rapid one-pot synthesis of pyran
annulated heterocyclic systems. Catal. Lett., 2005, 104, 39. (c)
Ranu, B. C.; Banerjee, S.; Roy, S. A task specific basic ionic liquid,
[Bmim]OH-promoted efficient, green and one-pot synthesis of
tetrahydrobenzo[b]pyran derivatives. Indian J. Chem. Sect. B Org.
Chem. Incl. Med. Chem., 2008, 47B, 1108.
Pot, clean synthesis of tetrahydrobenzo[b]pyran derivatives. Aust.
J. Chem., 2007, 60, 305.
(a) Jiang, B.; Chen Z. L.; Tang, X. X. Highly enantioselective
[17]
alkynylation of ꢀ-keto ester: an efficient method for constructing a
chiral tertiary carbon center. Org. Lett., 2002, 20, 3451. (b) Jiang,
B.; Chen, Z. L.; Xiong, W. N. Highly enantioselective alkynylation
of aldehydes catalyzed by a readily available chiral amino alcohol-
based ligand. Chem. Commun., 2002, 14, 1524. (c)Jiang, B.; Si, Y.
G. The first highly enantioselective alkynylation of chloral: a
practical and efficient pathway to chiral trichloromethyl propargyl
alcohols. Adv. Synth. Catal., 2004, 346, 669.
Shan, Z. X.; Wan, B. Y.; Wang, G. P. A highly efficient
chemoselective cyclocondensation of threo-(1S,2S)-2-amino-1-(4-
nitrophenyl)-1,3-propanediol with ketones and isomerization of the
condensates. Helv. Chim. Acta, 2002, 85, 1062.
[7]
[18]
[19]
(a) Shan, Z. X.; Lu, G. J. Selective oxidation of polyfunctional 2-
amino-1,3-propanediol derivatives. J. Org. Chem., 2004, 69, 3593.
(b) Shan, Z. X.; Lu, G. J. A new selective oxidation of N-methyl to
N-formyl upon threo-(1S,2S)-2-(N,N-dimethyl-amino)-1-(4’nitro-
phenyl)-1,3-propanediol. Chin. J. Org. Chem., 2004, 24, 325.
(a) Ha, W. Z.; Shan, Z. X. An economic, practical access to
enantiopure 1,10-bi-2-naphthols: enantioselective complexation
of threo-(1S,2S)-N-benzyl-N,N-dimethyl[1,3-dihydroxy-1-(4-nitro-
phenyl)]-2-propylammonium chloride. Tetrahedron Asymmetry,
2006, 17, 854. (b) Liu, D. J.; Shan, Z. X.; Liu, F.; Xiao, C. G.; Lu,
G. J.; Qin, J. G. A new and practical method for preparing
enantiomerically pure [1,1’-binaphthalene]-2,2’-diol: resolution of
racemic [1,1’-binaphthalene]-2,2’-diol with threo-(1S,2S)-2-amino-
[8]
[9]
[20]
1-(4-nitrophenyl)propane-1,3-diol_cyclohexanone
conden-sate.
Helv. Chim. Acta, 2003, 86, 157.
[21]
(a) Shan, Z. X.; Wan, B. Y. Preparation of S-ibuprofen. Faming
Zhuanli Shenqing Gongkai Shuomingshu, 2001, CN 1318537. (b)
Shan, Z. X. Method for preparation (S)-ibuprofen. Faming Zhuanli
Shenqing Gongkai Shuomingshu, 2001, CN 1326921.
Ha, W. Z.; Shan, Z. X. A New, Readily available double-
component system for asymmetric henry reaction. Lett. Org.
Chem., 2008, 5, 79.
Song, S. J.; Shan, Z. X.; Jin, Y. One-pot synthesis of
hexahydroquinolines via hantzsch four-component reaction
catalyzed by a cheap amino alcohol. Synth. Commun., 2009,
(accepted).
[10]
(a) Jin, T. S.; Wang, A. Q.; Wang, X.; Zhang, J. S.; Li, T. S. A
clean one-pot synthesis of tetrahydro-benzo[b]pyran derivatives
catalyzed by hexadecyl-trimethyl ammonium bromide in aqueous
media. Synlett, 2004, 871. (b) Shi, D.; Mou, J.; Zhuang, Q.; Wang,
X. One-pot synthesis of 2-amino-4-aryl-5-oxo-5,6,7,8-tetrahydro-
4H-1-benzopyran-3-carbonitriles in aqueous media. J. Chem. Res.,
2004, 821. (c) Gao, S.; Tsai, C. H.; Tseng, C.; Yao C. F. Fluoride
ion catalyzed multicomponent reactions for efficient synthesis of
4H-chromene and N-arylquinoline derivatives in aqueous media.
Tetrahedron, 2008, 64, 9143. (d) Jin, T. S.; Xiao, J. C.; Wang, S. J.;
Li, T. S.; Song, X. R. An efficient and convenient approach to the
synthesis of benzopyrans by a three-component coupling of one-pot
reaction. Synlett, 2003, 2001.
[22]
[23]
[24]
[25]
Nesterov, V. N.; Kislyi, V. P.; Sabutis, J. L.; Nesterov, V. V.;
Wiedenfeld, D. J.; Semenov, V. V. 2-Amino-4-(2-methoxyphenyl)-
7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile
and
2-amino-4-(2-methoxyphenyl)-7,7-dimethyl-3-nitro-4,6,7,8-
tetrahydro-5H-chromen-5-one hemihydrate. Acta Crystallogr.,
Section C Cryst. Struct. Commun., 2005, C61, o741.
Spectral data for the selected compounds:
[11]
Balalaie, S.; Bararjanian, M.; Amani, A. M.; Movassagh, B. (S)-
praline as a neutral and efficient catalyst for the one-pot synthesis
of tetrahydro benzo[b]pyran derivatives in aqueous media. Synlett,
2006, 263.
2-amino-4-(4-chlorophenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahy-
drochromene-3-carbonitrile (4c) 1H NMR (300 MHz, d6-DMSO):
ꢀ 7.26 (d, J = 8.1 Hz, 2H), 7.18 (d, J = 8.1 Hz, 2H), 4.57 (s, 2H),
4.39 (s, 1H), 2.45 (s, 2H), 2.22 (m, 2H), 1.11 (s, 3H), 1.03 (s, 3H);
13C NMR (75 MHz, d6-DMSO): ꢀ 200.5 161.9, 158.3, 142.6, 131.8,
128.7, 128.0, 119.2, 112.9, 59.1, 50.2, 35.0, 31.7, 28.5, 27.1; IR
(KBr): 3381, 2188, 1685, 1674, 1365, 1216 cm-1.
2-amino-4-(3-bromophenyl)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahy-
drochromene-3-carbonitrile (4g) 1H NMR (300 MHz, d6-
DMSO): ꢀ 7.36 (d, J = 7.8 Hz, 1H), 7.27 (s, 1H), 7.22 (d, J = 5.7
Hz, 1H), 7.13 (d, J = 7.5 Hz, 1H), 7.06 (s, 2H), 4.17 (s, 1H), 2.49
(s, 2H), 2.06-2.25 (m, 2H), 1.10 (s, 3H), 0.92 (s, 3H); 13C NMR (75
MHz, d6-DMSO): ꢀ 200.9, 168.0, 163.7, 152.6, 135.8, 135.1, 134.7,
131.5, 126.7, 124.7, 117.2, 62.8, 55.1, 40.5, 37.0, 33.5, 31.9; IR
(KBr): 3345, 2192, 1684, 1669, 1372, 1216 cm-1.
[12]
[13]
Wang, L. M.; Shao, J. H.; Tian, H.; Wang, Y. H.; Liu, B. Rare
earth perfluorooctanoate [RE(PFO)3] catalyzed one-pot synthesis
of benzopyran derivatives. J. Fluorine Chem., 2006, 127, 97.
(a) Fotouhi, L.; Heravi, M. M.; Fatehi, A.; Bakhtiari, K.
Electrogenerated base-promoted synthesis of tetrahydrobenzo
[b]pyran derivatives. Tetrahedron Lett., 2007, 48, 5379. (b)
Abdelrazek, F. M.; Metz, P.; Kataeva1, O.; Jäger1, A.;
El-Mahrouky, S. F. Synthesis and molluscicidal activity of new
chromene and pyrano[2,3-c]pyrazole derivatives. Arch. Pharm.
Chem. Life Sci., 2007, 340, 543. (c) Abdelrazeka, F. M.; Metza, P.;
Farrag, E. K. Synthesis and molluscicidal activity of 5-oxo-5,6,7,8-
tetrahydro-4H-chromene derivatives. Arch. Pharm. Pharm. Med.
Chem., 2004, 337, 482. (d) Abdelrazek, F. M.; Metwally, N. H.;
Sobhy, N. A. Synthesis and molluscicidal activity of some newly
substituted chromene and pyrano[2,3-c] pyrazole derivatives.
Afinidad, 2008, 65 (538), 482.
Bhosale, R. S.; Magar, C. V.; Solanke, K. S.; Mane, S. B.;
Choudhary, S. S.; Pawar, R. P. A Convenient Synthesis of 5-Oxo-
5,6,7,8-tetrahydro-4H-benzo-[b]-pyran derivatives catalyzed by
KF-alumina. Synth. Commun., 2003, 33, 119.
Das, B.; Krishnaiah, M.; Laxminarayana, K.; Damodar, K.; Kumar,
D. N. Silica-supported phosphomolybdic acid-catalyzed efficient
synthesis of 1,8-dioxooctahydroxanthene and tetrahydro- chromene
derivatives. Chem. Lett., 2008, 37, 1000.
2-amino-4-(4-dimethylaminophenyl)-7,7-dimethyl-5-oxo-5,6,7,
1
8-tetrahydrochromene-3-carbonitrile (4o) H NMR (300 MHz,
d6-DMSO): ꢀ 6.95 (d, J = 7.5 Hz, 2H), 6.87 (2H, s), 6.63 (d, J =
7.5 Hz, 2H), 4.05 (s, 1H), 2.84 (s, 6H), 2.48 (d, J = 5.1 Hz, 2H),
2.10-2.21 (m, 2H), 1.03 (s, 3H), 0.95 (s, 3H); 13C NMR (75 MHz,
d6-DMSO): ꢀ 200.9, 167.1, 163.6, 154.5, 137.8, 133.0, 125.2,
118.5, 117.6, 64.2, 55.3, 39.8, 37.0, 33.7, 32.0; IR (KBr): 3383,
3321, 2191, 1681, 1666, 1368, 1213 cm-1.
Crystallographic data for 4q: empirical formula, C16H16N2O3;
formula weight, 284.31; calculated density, 1.271 g/cm3; volume
(V), 1485.6(3) ꢁ3; crystal system, Monoclinic; space group,
P2(1)/c; Z = 4; unit cell dimensions, a =10.8394 (12) ꢁ, b =
9.2687(10) ꢁ, c = 14.9186(16) ꢁ, ꢀ = 97.615(2)˚, absorption
[14]
[15]
[16]
[26]
Bandgar, S. B.; Bandgar, B. P.; Korbad, B. L.; Totre, J. V.; Patil, S.
Uncatalyzed reactions in aqueous media: three-component, one-