Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2005(18): 3179-3180
DOI: 10.1055/s-2005-872177
DOI: 10.1055/s-2005-872177
PSP
© Georg Thieme Verlag Stuttgart · New York
Preparation of 3-Oxocyclohex-1-ene-1-carbonitrile
Further Information
Received
3 May 2005
Publication Date:
17 August 2005 (online)
Publication History
Publication Date:
17 August 2005 (online)
Abstract
Chromium trioxide oxidation of cyclohexenecarbonitrile efficiently provides analytically pure 3-oxocyclohex-1-ene-1-carbonitrile. The procedure is described in detail, providing a very reliable, one-step synthesis of a highly versatile oxonitrile.
Key words
oxonitrile - nitrile - oxidation - synthesis
-
1a
Cantrell TS. Tetrahedron 1971, 27: 1227 -
1b
Agosta WC.Lowrance WW. Tetrahedron Lett. 1969, 3053 - 2
Serebryakov EP.Kulomzina-Pletneva SD.Margaryan AK. Tetrahedron 1979, 35: 77 - 3
Yang WQ.Chen SZ.Huang L. Chin. Chem. Lett. 1998, 9: 233 ; Chem. Abstr. 1999, 131: 736759 - 4
Fleming FF.Zhang Z.Wang Q.Steward OW. Angew. Chem. Int. Ed. 2004, 43: 1126 - 5
Fleming FF.Wang Q.Steward OW. J. Org. Chem. 2003, 68: 4235 - 6
Fleming FF.Zhang Z.Wei G.Steward OW. Org. Lett. 2005, 7: 447 -
7a
Wang Y.Doering WVE.Staples RJ. J. Chem. Crystallogr. 1999, 29: 977 -
7b
Cronyn MW.Goodrich JE. J. Am. Chem. Soc. 1952, 74: 3331 - 8
Agosta WC.Lowrance WW. J. Org. Chem. 1970, 35: 3851 - 10
Nakai T.Tomooka K. In Encyclopedia of Reagents for Organic Synthesis Vol. 3:Paquette LA. Wiley; Chichester: 1995. p.1779 - 11
Nicolaou KC.Gray DLF.Montagnon T.Harrison ST. Angew. Chem. Int. Ed. 2002, 41: 996 - 12
Zimmerman HE.Pasteris RJ. J. Org. Chem. 1980, 45: 4864 -
13a
Johnson JN. In Encyclopedia of Reagents for Organic Synthesis Vol. 2:Paquette LA. Wiley; Chichester: 1995. p.1275-1277 -
13b
Lee TV. In Comprehensive Organic Synthesis Vol. 7:Fleming I.Trost BM. Pergamon; Oxford: 1991. p.291-303 -
13c
Salmond WG.Barta MA.Havens JL. J. Org. Chem. 1978, 43: 2057 - 14
Mousseron M.Jacquier R.Fontaine A.Zagdoun R. Bull. Soc. Chim. Fr. 1954, 1247 - 15
Kurihara T.Miki M.Yoneda R.Harusawa S. Chem. Pharm. Bull. 1986, 34: 2747 - 16 Attempts to optimize the selenium dioxide oxidation of 1 afforded low yields of 2 despite excellent results with related unsaturated esters:
Bestmann HJ.Schobert R. Angew. Chem., Int. Ed. Engl. 1985, 24: 791 - 17
Yu J.-Q.Wu H.-C.Corey EJ. Org. Lett. 2005, 7: 1415 -
18a Attempted oxidation with hydrogen peroxide and chromium hexacarbonyl is ineffective:
Pearson AJ.Chen Y.-S.Han GR.Hsu S.-Y.Ray T. J. Chem. Soc., Perkin Trans. 1 1985, 267 -
18b
The lack of oxidation may be due to competitive metal ligation of the nitrile as occurs with dirhodium(II) caprolactamate: Doyle M. P. personal communication.
-
18c For a related oxidation see:
Catino AJ.Forslund RE.Doyle MP. J. Am. Chem. Soc. 2004, 126: 13622
References
Available from Organometallics Inc.
19Assaying several different solvent mixtures identified CH2Cl2-hexanes (1.5:1) as optimal, although a stepped EtOAc-hexanes gradient (3:17, 1:4, 1:3) permitted isolation of 2.30 g of 2 in 64% yield.