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Synthesis 2002(14): 1987-1992
DOI: 10.1055/s-2002-34383
DOI: 10.1055/s-2002-34383
PAPER
© Georg Thieme Verlag Stuttgart · New York
Transition Metal-Promoted Synthesis of Functionalized and Unfunctionalized Pyridylallenes
Further Information
Received
14 June 2002
Publication Date:
26 September 2002 (online)
Publication History
Publication Date:
26 September 2002 (online)
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Abstract
The SN2′-substitution of several functionalized and unfunctionalized pyridyl-substituted propargylic acetates with the magnesium cuprate MeMgCl·CuI·LiBr and with phenylzinc chloride in the presence of catalytic amounts of Pd(PPh3)4 is examined. The copper-mediated substitution gives the desired pyridylallenes with good yield only if chelate formation between substrate and cuprate is not possible. In contrast, both chelating and non-chelating propargylic acetates can be converted efficiently into the corresponding pyridyl allenes under palladium catalysis.
Key words
allenes - copper - zinc - palladium - pyridines
- 1
Thorand S.Vögtle F.Krause N. Angew. Chem. Int. Ed. 1999, 38: 3721 ; Angew. Chem. 1999, 111, 3929 -
2a
Macdonald TL.Reagan DR. J. Org. Chem. 1980, 45: 4740 -
2b
Laux M.Krause N.Koop U. Synlett 1996, 86 - For 2-allenyl-substituted pyridines, see:
-
3a
Cherkasov LN.Bal’yan KV. Russ. J. Org. Chem. 1965, 1: 1843 -
3b
Al-Arnaout A.Courtois G.Miginiac L. J. Organomet. Chem. 1987, 333: 139 -
3c
Schmittel M.Strittmatter M.Vollmann K.Kiau S. Tetrahedron Lett. 1996, 37: 999 -
3d
Langer P.Doering M.Seyferth D.Goerls H. Chem.-Eur. J. 2001, 7: 573 - For 3-allenyl-substituted pyridines, see:
-
4a
Birtwistle I.Rogers V. J. Chem. Soc. Perkin Trans. 1 1987, 1347 -
4b
Reynolds KA.Dopico P.Brody MS.Finn MG. J. Org. Chem. 1997, 62: 2564 -
4c
Grigg R.Monteith M.Sridharan V.Terrier C. Tetrahedron 1998, 54: 3885 - 5For 4-allenyl-substituted pyridines, see:
- 5
Chan PCY.Jarman M.Wang MF.Potter GA. Tetrahedron Lett. 2000, 41: 2447 -
6a
Luong TJ.Linstrumelle G. Tetrahedron Lett. 1980, 21: 5019 -
6b
Ruitenberg K.Kleijn H.Elsevier CJ.Meijer J.Vermeer P. Tetrahedron Lett. 1981, 22: 1451 -
6c
Elsevier CJ.Stehouwer PM.Westmijze H.Vermeer P. J. Org. Chem 1983, 48: 1103 -
6d
Keinan E.Bosch E. J. Org. Chem. 1986, 51: 4006 -
6e
Konno T.Tanikawa M.Ishihara T.Yamanaka H. Chem. Lett. 2000, 1360 - 7
Krause N.Seebach D. Chem. Ber. 1987, 120: 1845 -
8a
Höfle G.Steglich W. Synthesis 1972, 619 -
8b
Höfle G.Steglich W.Vorbrüggen H. Angew. Chem. Int. Ed. Engl. 1978, 17: 569 ; Angew. Chem. 1978, 90, 602 - 9
Bolm C.Ewald M.Felder M.Schlinghoff G. Chem. Ber. 1992, 125: 1169 - 10
Parks JE.Wagner BE.Holm RH. Inorg. Chem. 1971, 10: 2472