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Synlett 2004(12): 2224-2226  
DOI: 10.1055/s-2004-831339
LETTER
© Georg Thieme Verlag Stuttgart · New York

KF-Alumina-Mediated Selective Double Michael Additions of Aryl Methyl Ketones: A Facile Entry to the Synthesis of Functionalized Pimelate Esters and Derivatives

Basudeb Basu*, Pralay Das, Ismail Hossain
Department of Chemistry, North Bengal University, Darjeeling 734 430, India
e-Mail: basu_nbu@indiatimes.com;
Further Information

Publication History

Received 17 May 2004
Publication Date:
03 September 2004 (online)

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Abstract

Here we describe simple and efficient double Michael additions of aromatic and aliphatic methyl ketones to electron deficient alkenes promoted on a surface of KF-alumina. This one-pot procedure provides an easy access to a host of functionalized pimelate esters, which can be subsequently converted in to 3-acylcyclohexanones.

Key words

double Michael additions - acetophenone - KF-alu­mina - pimelate esters - cyclohexanones

    References

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9

Representative Experimental Procedure: A mixture of 4-methoxyacetophenone (300 mg, 2 mmol) and ethyl acrylate (600 mg, 6 mmol) was added in one portion to dry preformed KF-alumina (2 g) and the solid mixture was stirred at 60 °C for 10 h. TLC was checked and the mixture was packed on a column of silica gel and eluted with petroleum ether-EtOAc (9:1) to afford diethyl (4-methoxybenzoyl) heptanedioate as colorless viscous oil (553 mg, 79%). IR (neat): 1735, 1680, 1588 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.22 (t, 6 H, J = 7.1 Hz, 2 OCH2CH 3 ), 1.80-1.88 (m, 2 H, 2 CHCH2CO), 2.05-2.12 (m, 2 H, 2 CHCH2CO), 2.19-2.41 (m, 4 H, 2 CH2CH 2CO), 3.56-3.63 (m, 1 H, COCHCH2), 3.87 (s, 3 H, OCH 3 ), 4.10 (q, 4 H, J = 7.1 Hz, 2 OCH 2 CH3), 6.95 (d, 2 H, J = 8.8 Hz, ArH), 7.99 (d, 2 H, J = 8.8 Hz, ArH). 13C NMR (75 MHz, CDCl3): δ = 14.0, 26.9, 31.5, 43.2, 55.3, 60.2, 113.8, 129.9, 130.6, 163.6, 172.9, 201.2.