Synthesis of Ferrocene Amides and α-Ketoamides via Palladium-Catalyzed Homogeneous Carbonylation Reaction

Zsolt Szarka; Rita Skoda-Földes; Árpád Kuik; Zoltán Berente; László Kollár

doi:10.1055/s-2003-37659

PAPER

Synthesis of Ferrocene Amides and α-Ketoamides via Palladium-Catalyzed Homogeneous Carbonylation Reaction

Zsolt Szarka^a, Rita Skoda-Földes*^b, Árpád Kuik^b, Zoltán Berente^c, László Kollár^d
^a Research Group for Petrochemistry of the Hungarian Academy of Sciences, Egyetem u. 8., P.O.Box 158, 8200 Veszprém, Hungary
^b University of Veszprém, Department of Organic Chemistry, Egyetem u. 8., P.O.Box 158, 8200 Veszprém, Hungary
Fax: 36(88)422022; e-Mail: skodane@almos.vein.hu;
^c University of Pécs, Institute of Biochemistry and Research Group for Chemical Sensors of the Hungarian Academy of Sciences, 7624 Pécs, Hungary
^d University of Pécs, Department of Inorganic Chemistry and Research Group for Chemical Sensors of the Hungarian Academy of Sciences, Ifjúság u. 6. (P.O.Box 266) 7624 Pécs, Hungary

Abstract

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Abstract

New ferrocene α-ketoamides and various ferrocene amides have been synthesized in good yields via homogeneous catalytic carbonylation of iodoferrocene in the presence of secondary amines as nucleophiles. With sterically less hindered amines, the appropriate choice of conditions made it possible to produce either the amides or the α-ketoamides with good selectivity. The reaction of amines with sterically hindered amino groups led to the amides as main products.

Key words

carbonylations - catalysis - palladium - ferrocene amides - ferrocene α-ketoamides

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References

<A NAME="RT10702SS-1">1</A> Togni A. Hayashi T. Ferrocenes VCH; Weinheim: 1995.

<A NAME="RT10702SS-2A">2a</A> Beer PD. Crane CG. Danks JP. Gale PA. McAleer JF. J. Organomet. Chem. 1995, 490: 143

<A NAME="RT10702SS-2B">2b</A> Brindley GD. Fox OD. Beer PD. J. Chem. Soc., Dalton Trans. 2000, 4354

<A NAME="RT10702SS-3A">3a</A> Kingston JE. Ashford L. Beer PD. Drew MGB. J. Chem. Soc., Dalton Trans. 1999, 251

<A NAME="RT10702SS-3B">3b</A> Valério C. Fillaut J.-L. Ruiz J. Guittard J. Blais J.-C. Astruc D. J. Am. Chem. Soc. 1997, 119: 2588

<A NAME="RT10702SS-4">4</A> Georgopoulou AS. Mingos DMP. White AJP. Williams DJ. Horrocks BR. Houlton A. J. Chem. Soc., Dalton Trans. 2000, 2969

<A NAME="RT10702SS-5A">5a</A> Degani Y. Heller A. J. Am. Chem. Soc. 1988, 110: 2615

<A NAME="RT10702SS-5B">5b</A> Badia A. Carlini R. Fernandez A. Battaglini F. Mikkelsen SR. English AM. J. Am. Chem. Soc. 1993, 115: 7053

<A NAME="RT10702SS-6">6</A> Laufer RS. Veith U. Taylor NJ. Snieckus V. Org. Lett. 2000, 2: 629

<A NAME="RT10702SS-7">7</A> Chesney A. Bryce MR. Chubb RWJ. Batsanov AS. Howard JKA. Tetrahedron: Asymmetry 1997, 8: 2337

<A NAME="RT10702SS-8">8</A> Galow TH. Rodrigo J. Cleary K. Cooke G. Rotello VM. J. Org. Chem. 1999, 64: 3745

<A NAME="RT10702SS-9">9</A> Watanabe M. Araki S. Butsugan Y. J. Org. Chem. 1991, 56: 2218

<A NAME="RT10702SS-10">10</A> Imrie C. Loubser C. Engelbrecht P. McCleland CW. J. Chem. Soc., Perkin Trans. 1 1999, 2513

<A NAME="RT10702SS-11">11</A> Plenio H. Hermann J. Sehring A. Chem.-Eur. J. 2000, 6: 1820

<A NAME="RT10702SS-12">12</A> Carlström AS. Frejd T. J. Org. Chem. 1990, 55: 4175

<A NAME="RT10702SS-13">13</A> Jackson RFW. Turner D. Block MH. Synlett 1996, 862

<A NAME="RT10702SS-14A">14a</A> Skoda-Földes R. Szarka Z. Kollár L. Dinya Z. Horváth J. Tuba Z. J. Org. Chem. 1999, 64: 2134

<A NAME="RT10702SS-14B">14b</A> Szarka Z. Skoda-Földes R. Kollár L. Horváth J. Tuba Z. Synth. Commun. 2000, 30: 1945

<A NAME="RT10702SS-14C">14c</A> Skoda-Földes R. Székvölgyi Z. Kollár L. Berente Z. Horváth J. Tuba Z. Tetrahedron 2000, 56: 3415

<A NAME="RT10702SS-15">15</A> Colquhoun HM. Thompson DJ. Twigg MV. In Carbonylation: Direct Synthesis of Carbonyl Compounds Plenum Press; New York: 1991.

<A NAME="RT10702SS-16A">16a</A> For a review see: Collin J. Bull. Soc. Chim. Fr. 1988, 976

<A NAME="RT10702SS-16B">16b</A> Yamamoto A. Bull. Chem. Soc. Jpn. 1995, 68: 433

<A NAME="RT10702SS-17">17</A> Szarka Z. Skoda-Földes R. Kollár L. Tetrahedron Lett. 2001, 42: 739

<A NAME="RT10702SS-18">18</A> Ozawa F. Soyama H. Yanagihara H. Aoyama I. Takino H. Izawa K. Yamamoto T. Yamamoto A. J. Am. Chem. Soc. 1985, 107: 3235

<A NAME="RT10702SS-19">19</A> Amatore C. Jutand A. M’Barki MA. Organometallics 1992, 11: 3009

<A NAME="RT10702SS-20">20</A> Ozawa F. Sugimoto T. Yuasa Y. Santra M. Yamamoto T. Yamamoto A. Organometallics 1984, 3: 683

MS data for 6: m/e (%) = 412 (100) [M⁺], 312 (32), 241 (75), 220 (42), 121 (33)

<A NAME="RT10702SS-22">22</A> Rausch MD. Ciappenelli DJ. J. Organomet. Chem. 1967, 10: 127

<A NAME="RT10702SS-23">23</A> IR spectrum corresponds well to literature data, see: Acton EM. Silverstein RM. J. Org. Chem. 1959, 24: 1487 and Ref. 8

<A NAME="RT10702SS-24A">24a</A> IR and MS spectra correspond well to literature data, see: Cox RL. Schneider TW. Koppang MD. Anal. Chim. Acta 1992, 262: 145

<A NAME="RT10702SS-24B">24b</A> Reshetova MD. Yankovski SA. Zh. Obshch. Khim. 1989, 59: 1450

<A NAME="RT10702SS-25">25</A> IR spectrum corresponds well to literature data, see: Katada T. Nishida M. Kato S. Mizuta M. J. Organomet. Chem. 1977, 129: 189

It has been obtained as a mixture of cis/trans dimethyl-piperidine isomers. The two sets of NMR signals have been assigned with the help of 2D NMR techniques (¹H-¹H ¹H-¹³C). Mass spectra is given according to GC-MS.

<A NAME="RT10702SS-27">27</A> Hammond PJ. Beer PD. Dudman C. Danks IP. Hall CD. J. Organomet. Chem. 1986, 306: 367