Abstract
An efficient method for the addition of trimethylsilylcyanide (TMSCN) to aldehydes using dispersed NbF5 as the catalyst is described. Cyano transfer from TMSCN to aldehydes occurs within 10 minutes at room temperature in the presence of 0.5 mol% of NbF5 under solvent-free conditions giving cyanohydrins in excellent yields of over 95%. These conditions are extremely mild, simple and tolerate various functional groups.
Key words
aldehydes - catalysis - green chemistry - cyanohydrins - solvent-free
References 1 Dr. G. Rajagopal is a Brain Pool Scientist from the Department of Chemistry, BSA Crescent Engineering College, Chennai 600 048, India. He was assisted by a grant from the Korean Federation of Science and Technology Societies and Korea Science and Engineering Foundation.
2a
North M.
Synlett
1993,
807
2b
Effenberger F.
Angew. Chem., Int. Ed. Engl.
1994,
33:
1555
2c
Gregory RJH.
Chem. Rev.
1999,
99:
3649
2d
Kobayashi S.
Ishitani H.
Chem. Rev.
1999,
99:
1069
2e
Gröger H.
Chem. Rev.
2003,
103:
2795
For achiral catalysts, see:
3a
Matsubara S.
Takai T.
Utimoto K.
Chem. Lett.
1991,
1447
3b
Whitesell JK.
Apodaca R.
Tetrahedron Lett.
1996,
37:
2525
3c
Yang Y.
Wang D.
Synlett
1997,
1379
3d
Saravanan P.
Anand RV.
Singh VK.
Tetrahedron Lett.
1998,
39:
3823
3e
Bandini M.
Cozzi PG.
Melchiorre P.
Umani-Ronchi A.
Tetrahedron Lett.
2001,
42:
3041
3f
Bandini M.
Cozzi PG.
Garelli A.
Melchiorre P.
Umani-Ronchi A.
Eur. J. Org. Chem.
2002,
3243
3g
Cordoba R.
Plumet J.
Tetrahedron Lett.
2003,
44:
6157
3h
Baleizão C.
Gigante B.
Garcia H.
Corma A.
Tetrahedron Lett.
2003,
44:
6813
3i
He B.
Li Y.
Feng X.
Zhang G.
Synlett
2004,
1776
3j
Iwanami K.
Oriyama T.
Chem. Lett.
2004,
33:
1324
3k
Itazaki M.
Nakazawa H.
Chem. Lett.
2005,
34:
1054
3l
Iwanami K.
Aoyagi M.
Oriyama T.
Tetrahedron Lett.
2006,
47:
4741
3m
Wada M.
Takahashi T.
Domae T.
Fukuma T.
Miyoshi N.
Smith K.
Tetrahedron: Asymmetry
1997,
8:
3939
3n
Azizi N.
Saidi MRJ.
Organomet. Chem.
2003,
688:
283
For chiral catalysts, see:
4a
Kobayashi S.
Tsuchiya Y.
Mukaiyama T.
Chem. Lett.
1991,
541
4b
Ohno H.
Nitta H.
Tanaka K.
Mori A.
Inoue S.
J. Org. Chem.
1992,
57:
6778
4c
Hayashi M.
Inoue T.
Miyamoto Y.
Oguni N.
Tetrahedron
1994,
50:
4385
4d
Bolm C.
Müller P.
Tetrahedron Lett.
1995,
36:
1625
4e
Holmes IP.
Kagan HB.
Tetrahedron Lett.
2000,
41:
7457
4f
Lundgren S.
Lutsenko S.
Jönsson C.
Moberg C.
Org. Lett.
2003,
5:
3663
4g
Li Y.
He B.
Qin B.
Feng X.
Zhang G.
J. Org. Chem.
2004,
69:
7910
4h
Liu Y.
Liu X.
Xin J.
Feng X.
Synlett
2006,
1085
4i
Belokon’ YN.
North M.
Parsons T.
Org. Lett.
2000,
2:
1617
4j
Kanai M.
Kato N.
Ichikawa E.
Shibasaki M.
Synlett
2005,
1491
4k
Chen F.-X.
Feng X.
Synlett
2005,
892
5
Brunel JM.
Holmes IP.
Angew. Chem. Int. Ed.
2004,
43:
2752
6a
Komatsu N.
Uda M.
Suzuki H.
Takahashi T.
Domae T.
Wada M.
Tetrahedron Lett.
1997,
38:
7215
6b
Loh T.-P.
Xu K.-C.
Ho DS.-C.
Sim K.-Y.
Synlett
1998,
369
6c
Vougioukas AE.
Kagan HB.
Tetrahedron Lett.
1987,
28:
5513
6d
Reetz MT.
Drewes MW.
Harms K.
Reif W.
Tetrahedron Lett.
1988,
29:
3295
6e
Evans DA.
Truesdale LK.
Carroll GL.
J. Chem. Soc., Chem. Commun.
1973,
55
7
Kurono N.
Yamaguchi M.
Suzuki K.
Ohkuma T.
J. Org. Chem.
2005,
70:
6530
8
Fetterly BM.
Verkade JG.
Tetrahedron Lett.
2005,
46:
8061
9
Wang L.
Huang X.
Jiang J.
Liu X.
Feng X.
Tetrahedron Lett.
2006,
47:
1581
10
Song JJ.
Gallou F.
Reeves JT.
Tan Z.
Yee NK.
Senanayake CH.
J. Org. Chem.
2006,
71:
1273
11
Suzuki Y.
Abu Bakar MD.
Muramatsu K.
Sato M.
Tetrahedron
2006,
62:
4227
12a
North M.
Tetrahedron: Asymmetry
2003,
14:
147
12b
Belokon YN.
Ishibashi E.
Nomura H.
North M.
Chem. Commun.
2006,
1775
12c
Hamashima Y.
Sawada D.
Kanai M.
Shibasaki M.
J. Am. Chem. Soc.
1999,
121:
2641
12d
Hamashima Y.
Sawada D.
Nogami H.
Kanai M.
Shibasaki M.
Tetrahedron
2001,
57:
805
12e
Casas J.
Najera C.
Sansano JM.
Saa JM.
Org. Lett.
2002,
4:
2589
12f
Furest DE.
Jacobsen EN.
J. Am. Chem. Soc.
2005,
127:
8964
12g Special symposium for the synthesis of non-racemic cyanohydrins, see: Tetrahedron
2004,
60:
10371
13a
Kim SS.
Song DH.
Eur. J. Org. Chem.
2005,
1777
13b
Kim SS.
Kwak JM.
Tetrahedron
2006,
62:
49
13c
Kim SS.
Lee SH.
Kwak JM.
Tetrahedron: Asymmetry
2006,
17:
1165
13d
Kim SS.
Lee SH.
Synth. Commun.
2005,
35:
751
13e
Kim SS.
Pure. Appl. Chem.
2006,
78:
977
14a
Kim SS.
Rajagopal G.
Song DH.
J. Organomet. Chem.
2004,
689:
1734
14b
Kim SS.
Kim DW.
Rajagopal G.
Synthesis
2004,
213
14c
Kim SS.
Rajagopal G.
Kim DW.
Song DH.
Synth. Commun.
2004,
34:
2973
15a
Clark JH.
Catalysis of Organic Reactions using Supported Inorganic Reagents
VCH;
New York:
1994.
15b
Chemistry of Waste Minimization
Clark JH.
Chapman and Hall;
London:
1995.
16a
Howrath J.
Gillespie K.
Tetrahedron Lett.
1996,
37:
6011
16b
Andrade CKZ.
Azevedo NR.
Tetrahedron Lett.
2001,
42:
6473
16c
Arai S.
Sudo Y.
Nishida A.
Synlett
2004,
1104
17
Karmi B.
MaMani L.
Org. Lett.
2004,
6:
4813
18
Kantham ML.
Sreekanth P.
Shanthi PL.
Green Chem.
2000,
2:
47