Synthesis, Table of Contents PAPER © Georg Thieme Verlag Stuttgart · New York A Simple and Direct Access to Ethylidene Malonates Maité Sylla, Delphine Joseph, Emilie Chevallier, Cheikhou Camara, Françoise Dumas*Laboratoire de Synthèse de Composés d’Intérêt Biologique, BioCIS, Unité associée au CNRS, Centre d’Etudes Pharmaceutiques, Université Paris Sud, 5 rue Jean-Baptiste Clément, 92296 Châtenay-Malabry Cedex, FranceFax: +33(1)46835752; e-Mail: francoise.dumas@cep.u-psud.fr; Recommend Article Abstract Buy Article All articles of this category Abstract The condensation of active methylene compounds 1 with acetaldehyde was efficiently promoted by a catalytic amount of lithium bromide in the presence of acetic anhydride to give ethylidene malonates 2 in 77-97% yield. Key words Knoevenagel condensations - catalysis - aldol reactions - aldehydes - substituent effects Full Text References References 1a d’Angelo J. Desmaële D. Dumas F. Guingant A. Tetrahedron: Asymmetry 1992, 3: 459 1b d’Angelo J. Cavé C. Desmaële D. Dumas F. In Trends in Organic Chemistry Vol. 4: Pandalai SG. Trivandrum; India: 1993. p.555 2a Camara C. Joseph D. Dumas F. d’Angelo J. Charoni A. Tetrahedron Lett. 2002, 42: 1445 2b de Oliveira ER. Miet C. d’Angelo J. Dumas F. In Chemical Processes and Reactions under Extreme or Non-Classic Conditions Luche JL. Balny C. Benefice S. Denis JM. Pétrier C. Office for Official Publications of the European Communities; Luxembourg: 1998. p.97 2c Camara C. Keller L. Jean-Charles K. Joseph D. Dumas F. High Pres. Res. 2004, 24: 149 3 Also see: Jabin I. Revial G. Monnier-Benoit N. Netchitailo P. J. Org. Chem. 2001, 66: 256 4a For a review, see: Jones G. In Organic Reactions Vol. 15: Wiley; New York: 1967. p.204 4b Brettle R. In Comprehensive Organic Chemistry Vol. 1: Stoddart JF. Pergamon Press; Oxford UK: 1979. p.943 ; see page 967 4c Tiezte LF. Beifuss U. In Comprehensive Organic Synthesis Trost BM. Fleming I. Pergamon Press; Oxford UK: 1991. p.341 5 Chodroff S. Whitmore WF. J. Am. Chem. Soc. 1950, 72: 1073 6 See for example: Cardillo G. Fabbroni S. Gentilucci L. Gianotti M. Tolomelli A. Synth. Commun. 2003, 33: 1587 7a Kaupp G. Naimi-Jamal MR. Schmeyers J. Tetrahedron 2003, 59: 3753 7b McCluskey A. Robinson PJ. Hill T. Scott JL. Edwards JK. Tetrahedron Lett. 2002, 43: 3117 8a Texier-Boulet F. Foucaud A. Tetrahedron Lett. 1982, 23: 4927 8b Cooke G. Palmer HM. Schultz O. Synth. Commun. 1996, 2549 8c Cabello JA. Campelo JM. Garcia A. Luna D. Marinas JM. J. Org. Chem. 1984, 49: 5195 8d Angeletti E. Canapa C. Martinetti G. Venturello P. Tetrahedron Lett. 1993, 34: 7437 9 Brufola G. Fringuelli F. Piernatti O. Pizzo F. Heterocycles 1997, 45: 1715 10a Mitra AK. De A. Karchaudhuri N. Synth. Commun. 1999, 29: 2731 10b Cherouvrier JR. Boisset J. Carreaux F. Bazureau JP. Green Chem. 2001, 3: 165 11 Jenner G. Tetrahedron Lett. 2001, 42: 243 12 Morrisson DW. Forbes DC. Davis JH. Tetrahedron Lett. 2001, 42: 6053 13a Liu HN. Auchus R. Walsh CT. J. Am. Chem. Soc. 1984, 106: 5335 13b Ishida A. Yamashita S. Takamuku S. Bull. Chem. Soc. Jpn. 1988, 61: 2229 14a Lehnert W. Tetrahedron Lett. 1970, 34: 4723 14b Lehnert W. Tetrahedron 1972, 28: 663 14c Lehnert W. Tetrahedron 1973, 29: 635 14d Compare: Jones G. Org. React. (N.Y.) 1967, 15: 204 15 Taken from the web page available at: http://daecr1.harvard.edu/pdf/evans_pKa_table.pdf. 16 Weir MRS. Hyne JB. Can. J. Chem. 1965, 43: 772 17 Prajapati G. Lekhok KC. Sandhu JS. Ghosh AC. J. Chem. Soc., Perkin Trans 1 1996, 959 18a Wingler F. Reiff H. Liebigs Ann. Chem. 1967, 705: 96 18b Yamamoto Y. Nishii S. J. Org. Chem. 1988, 53: 3597 18c Bogdanov VS. Ugrak BI. Krasnaya ZA. Stytsenko TS. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.) 1990, 298 For a synthesis and reactivity of aldol 4c, see for example: 19a Roesch A. Bull. Soc. Chim. 1937, 4: 1643 19b Brink M. Schjanberg E. J. Prakt. Chem. 1980, 685 19c Ref. 13b. 20 Lopez Giral A. Mahuteau-Betzer F. Gateau-Olesker A. Marazano C. Eur. J. Org. Chem. 2003, 1859 21 Doleschall G. Acta Chim. Hung. 1991, 128: 823 22 Bégué J.-P. Bonnet-Delpon D. Crousse B. Synlett 2004, 18 23a A partial conversion was observed after 12 h at 80 °C (1a:7 = 3:1). No trace of ethylidene diacetate 5 could be detected in the crude. 23b Cardillo G. Gentilucci L. Gianotti M. Perciaccante R. Tolomelli A. J. Org. Chem. 2001, 66: 8657 23c Tsuboi S. Wada H. Murakana K. Takeda A. Bull. Chem. Soc. Jpn. 1987, 60: 2917 24a Matsuki T. Hu NX. Aso Y. Otsubo T. Ogura F. Bull. Chem. Soc. Jpn. 1989, 62: 2105 24b Niwayama S. Houk KN. Kusumi T. Tetrahedron Lett. 1994, 35: 527
