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DOI: 10.1055/s-2003-39162
Triphenylphosphine Catalyzed Michael Addition of Oximes onto Activated Olefins [1]
Publication History
Publication Date:
09 May 2003 (online)
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Abstract
A new reaction condition for Michael addition of oximes onto activated olefins has been discovered using a catalytic amount of triphenylphosphine. This is a first and milder alternative to classical base (hydroxide, alkoxide) catalyzed Michael addition of oximes. Various aldoximes 1a-h and ketoximes 2a-c (Figure [1] ) were reacted with different Michael acceptors such as ethyl acrylate, acrylonitrile, phenyl vinyl sulfone, methyl vinyl ketone, and 1-nitrocyclohex-1-ene to obtain the corresponding Michael adducts. About 35 different examples were attempted (Table [1] and Scheme [1] ); except in six cases where reactions did not produce desired products, yields varied from good to excellent. Reactions without triphenylphosphine did not proceed. A plausible mechanism of catalytic action in the present reactions is proposed (Figure [2] ).
Key words
Michael additions - oximes - alkenes - phosphorus - catalysis
DRL Publication No. 284.
- 2
Jung ME. In Comprehensive Organic Synthesis Vol. 4:Trost BM.Flemming I. Pergamon; Oxford: 1991. p.30-39 ; and references therein -
3a
Kobayashi S.Kakamuto K.Sugiura M. Org. Lett. 2002, 4: 1319 -
3b
Kolarovic A.Berke D.Baran P.Povazanec F. Tetrahedron Lett. 2001, 42: 2579 -
3c
Shaikh NS.Deshpande VH.Bedekar AV. Tetrahedron 2001, 57: 9045 -
3d
Bartoli G.Bosco M.Marcantoni E.Petrini M.Sambri L.Torregiani E. J. Org. Chem. 2001, 66: 9052 - 4
Grimaud L.Rotulo D.Ros-Perez R.Guitry-Azam L.Prunet J. Tetrahedron Lett. 2002, 43: 7477 -
5a
Kamimura A.Murakami N.Yokota K.Shirai M.Okamoto H. Tetrahedron Lett. 2002, 43: 7521 -
5b
Skarřewski J.ZieliÒska-BŠajet M.Turowska-Tyrk I. Tetrahedron: Asymmetry 2001, 12: 1923 -
5c
Nishide K.Miyamoto T.Kumar K.Ohsugu S.Node M. Tetrahedron Lett. 2002, 43: 8569 -
5d
Abrouki Y.Zahouily M.Rayadh A.Bahlaouan B.Sebti S. Tetrahedron Lett. 2002, 43: 8951 - 6
Keglevich G.Sipos M.Imre T.Ludányi K.Szieberth D.Tıke L. Tetrahedron Lett. 2002, 43: 8515 - 7
Mukaiyama T.Hata T. Bull. Chem. Soc. Jpn. 1960, 1712 - 8
Newman MS.Junjappa H. J. Org. Chem. 1971, 36: 2606 - 9 As an example, see:
Macchia B.Balsamo A.Lapucci A.Macchia F.Martinelli A.Nencetti S.Orlandini E.Baldacci M.Mengozzi G.Soldani G.Domiano P. J. Med. Chem. 1990, 33: 1423 ; and references cited herein (for anti-inflammatory study). In this report, twenty different aldoximes and ketoximes were added to ethyl acrylate using KOH (16 mol%) as base catalyst in EtOH solvent. - 10 For recent medicinal chemistry on
oxime based compounds, see:
Takamura M.Yanagisawa H.Kanai M.Shibasaki M. Chem. Pharm. Bull. 2002, 50: 1118 - 11 Triphenylphosphine is known as a
catalyst for the Michael addition of carbon nucleophiles. Please
see:
Gómez-Bengoa E.Cuerva JM.Mateo C.Echavarren AM. J. Am. Chem. Soc. 1996, 118: 8553 ; and references cited therein - 12 For a recent report on triphenylphosphine
catalyzed Michael addition of carbon nucleophiles, see:
Lumbierres M.Marchi C.Moreno-Mañas M.Sebastian RM.Vallribera A.Lago E.Molins E. Eur. J. Org. Chem. 2001, 2321
References
DRL Publication No. 284.
13Oximes were prepared by reacting the corresponding carbonyl compounds with excess of hydroxylamine in methanol, either at r.t. or when required under heating (55 °C).