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Synthesis 2006(18): 2996-3002
DOI: 10.1055/s-2006-950198
DOI: 10.1055/s-2006-950198
PAPER
© Georg Thieme Verlag Stuttgart · New York
Efficient Oxidative Synthesis of 2-Oxazolines
Further Information
Received
02 June 2006
Publication Date:
21 August 2006 (online)
Publication History
Publication Date:
21 August 2006 (online)
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Abstract
New methodology for the synthesis of variously substituted 2-oxazolines and one dihydrooxazine using aldehydes, amino alcohols, and N-bromosuccinimide as an oxidizing agent is described. This one-pot synthesis is characterized by mild reaction conditions, broad scope, high yields, and its preparative simplicity.
Key words
amino alcohols - oxidative coupling - oxazolines - oxazolidines - N-bromosuccinimide
- 1
Andreasch R. Monatsh. Chem. 1884, 5: 33 -
2a
Gant TG.Meyers AI. Tetrahedron 1994, 50: 2297 ; and references cited therein -
2b
Ager DJ.Prakash I.Schaad DR. Chem. Rev. 1996, 96: 835 - 3
Greene TW.Wuts PGM. Protective Groups in Organic Synthesis 3rd ed.: Wiley; New York: 1999. - 4
Snieckus V. Chem. Rev. 1990, 90: 879 -
5a
Huang H.Hoogenboom R.Leenen MAM.Guillet P.Jonas AM.Schubert US.Gohy J.-F. J. Am. Chem. Soc. 2006, 128: 3784 -
5b
Kobayashi S.Fujikawa S.-i.Ohmae M. J. Am. Chem. Soc. 2003, 125: 14357 -
6a
Nicolaou KC.Lizos DE.Kim DW.Schlawe D.de Noronha RG.Longbottom DA.Rodriguez M.Bucci M.Cirino G. J. Am. Chem. Soc. 2006, 128: 4460 -
6b
Pirrung MC.Tumey LN.McClerren AL.Raetz CRH. J. Am. Chem. Soc. 2003, 125: 1575 -
6c
Bode HB.Irschik H.Wenzel SC.Reichenbach H.Müller R.Höfle G. J. Nat. Prod. 2003, 66: 1203 -
6d
Kline T.Andersen NH.Harwood EA.Bowman J.Malanda A.Endsley S.Erwin AL.Doyle M.Fong S.Harris AL.Mendelsohn B.Mdluli K.Raetz CRH.Stover CK.Witte PR.Yabannavar A.Zhu S. J. Med. Chem. 2002, 45: 3112 -
6e
Bergeron RJ.Xin MG.Weimar WR.Smith RE.Wiegand J. J. Med. Chem. 2001, 44: 2469 -
7a
Meyers AI.Shipman M. J. Org. Chem. 1991, 56: 7098 -
7b
Gnas Y.Glorius F. Synthesis 2006, 1899 -
8a
Ghosh AK.Mathivanan P.Cappiello J. Tetrahedron: Asymmetry 1998, 9: 1 -
8b
Pfaltz A. Acc. Chem. Res. 1993, 26: 339 -
8c
Helmchen G.Pfaltz A. Acc. Chem. Res. 2000, 33: 336 -
9a
Vorbrüggen H.Krolikiewicz K. Tetrahedron 1993, 49: 9353 -
9b
Appel R. Angew. Chem., Int. Ed. Engl. 1975, 14: 801 - 10
Witte H.Seeliger W. Justus Liebigs Ann. Chem. 1974, 996 -
11a
Neilson DG. In The Chemistry of Amidines and ImidatesPatai S. Wiley; London: 1975. p.389 -
11b For an alternative method, see:
Hoppe D.Schöllkopf U. Angew. Chem., Int. Ed. Engl. 1970, 9: 300 -
12a
Kawashita Y.Nakamichi N.Kawabata H.Hayashi M. Org. Lett. 2003, 5: 3713 -
12b
Chang J.Zhao K.Pan S. Tetrahedron Lett. 2002, 43: 951 -
12c
Varma RS.Kumar D. J. Heterocycl. Chem. 1998, 35: 1539 -
12d
Varma RS.Saini RK.Prakash O. Tetrahedron Lett. 1997, 38: 2621 -
12e
Park KH.Jun K.Shin SR.Oh SW. Tetrahedron Lett. 1996, 37: 8869 - Very recently, the first oxidative synthesis of imidazolines has been reported:
-
13a
Fujioka H.Murai K.Ohba Y.Hiramatsu A.Kita Y. Tetrahedron Lett. 2005, 46: 2197 - See also these related oxidation reactions:
-
13b
Fujioka H.Murai K.Ohba Y.Hirose H.Kita Y. Chem. Commun. 2006, 832 -
13c
Ishihara M.Togo H. Synlett 2006, 227 -
13d
Gogoi P.Konwar D. Tetrahedron Lett. 2006, 47: 79 -
14a Intramolecular redox reaction of 2-formylbenzaldehyde, see:
Shipchandler MT. J. Heterocycl. Chem. 1977, 14: 305 -
14b Reaction of aldehydes with 1,2-hydroxy azides, see:
Badiang JG.Aubé J. J. Org. Chem. 1996, 61: 2484 -
14c Synthesis of 3-oxazolines (with the formation of 2-oxazoline as minor byproducts), see:
Favreau S.Lizzani-Cuvelier L.Loiseau M.Duñach E.Fellous R. Tetrahedron Lett. 2000, 41: 9787 -
16a
Martinek T.Lazar L.Fülöp F.Riddell FG. Tetrahedron 1998, 54: 12887 -
16b
Agami C.Comesse S.Kadouri-Puchot C. J. Org. Chem. 2002, 67: 1496 - Related oxidations are known:
-
18a Convenient one-pot conversion of alcohols into esters via hemiacetal intermediates using Br2, see:
Lichtenthaler FW.Jarglis P.Lorenz K. Synthesis 1988, 790 -
18b Oxidation of isolated oxazolidines to oxazoles with NBS/(BzO)2 in refluxing CCl4, see:
Badr MZA.Aly MM.Fahmy AM.Mansour MEY. Bull. Chem. Soc. Jpn. 1981, 54: 1844 -
18c The oxidation of aldehydes to acid bromides requires more forcing conditions, see:
Cheung Y.-F. Tetrahedron Lett. 1979, 20: 3809 -
19a
Scully FEJ. J. Org. Chem. 1980, 45: 1515 -
19b
Bachmann WE.Cava MP.Dreiding AS. J. Am. Chem. Soc. 1954, 76: 5554 -
19c
Abou-Gharbia M.Ketcha DM.Zacharias DE.Swern D. J. Org. Chem. 1985, 50: 2224 -
20a
Mugesh G.Singh HB.Butcher RJ. Tetrahedron: Asymmetry 1999, 10: 237 -
20b
Cwik A.Hell Z.Hegedüs A.Finta Z.Horváth Z. Tetrahedron Lett. 2002, 43: 3985 -
21a
Koch G.Lloyd-Jones GC.Loiseleur O.Pfaltz A.Prétôt R.Schaffner S.Schnider P.von Matt P. Recl. Trav. Chim. Pays-Bas 1995, 114: 206 -
21b
Ikeda S.Kondo H.Arii T.Odashima K. Chem. Commun. 2002, 2422 -
21c
Bower JF.Martin CJ.Rawson DJ.Slawin AMZ.Williams JMJ. J. Chem. Soc., Perkin Trans. 1 1996, 333 - 22
Katritzky AR.Cai C.Suzuki K.Singh SK. J. Org. Chem. 2004, 69: 811 - 23
Lafargue P.Guenot P.Lellouche J.-P. Heterocycles 1995, 41: 947 - 24
Bates GS.Varelas MA. Can. J. Chem. 1980, 58: 2562 - 25
Kamata K.Agata I.Meyers AI. J. Org. Chem. 1998, 63: 3113 - 26
Lehr P.Billich A.Charpiot B.Ettmayer P.Scholz D.Rosenwirth B.Gstach H. J. Med. Chem. 1996, 39: 2060 - 27
Jones RAY.Katritzky AR.Record KAF.Scattergood R.Sullivan JM. J. Chem. Soc., Perkin Trans. 2 1974, 402 - 28
Brunner H.Obermann U. Chem. Ber. 1989, 122: 499 - 29
Totleben MJ.Prasad JS.Simpson JH.Chan SH.Vanyo DJ.Kuehner DE.Deshpande R.Kodersha GA. J. Org. Chem. 2001, 66: 1057 - 30
Elliott MC.Kruiswijk E. J. Chem. Soc., Perkin Trans. 1 1999, 3157 - 31
Yamauchi M.Itai K.Honda Y. Chem. Pharm. Bull. 2002, 50: 1255 -
32a
Bandgar BP.Pandit SS. Tetrahedron Lett. 2003, 44: 2331 -
32b
Serota S.Simon JR.Murray EB.Linfield WM. J. Org. Chem. 1981, 46: 4147 - 33
Wipf P.Hayes GB. Tetrahedron 1998, 54: 6987
References
This work was first presented on the BASF Catalysis Award Symposium, in Heidelberg, Germany, July 8 2005.
17More highly substituted amino alcohols have not been tested.