Indium-Mediated Reformatsky-Type Reaction of β-Aminovinyl Chlorodifluoro­methyl Ketones with Heteroaryl Aldehydes

Maurice  Médebielle; Osamu  Onomura; Robert  Keirouz; Etsuji  Okada; Hirokazu  Yano; Terukazu  Terauchi

doi:10.1055/s-2002-35618

SPECIALTOPIC

Indium-Mediated Reformatsky-Type Reaction of β-Aminovinyl Chlorodifluoromethyl Ketones with Heteroaryl Aldehydes

Maurice Médebielle*^a, Osamu Onomura^a, Robert Keirouz^a, Etsuji Okada^b, Hirokazu Yano^b, Terukazu Terauchi^b
^a Université Claude Bernard-Lyon 1 (UCBL), Laboratoire Synthèse, Electrosynthèse et Réactivité des Composés Organiques Fluorés (SERCOF), UMR CNRS-UCBL 5622, Bâtiment E. Chevreul, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France
Fax: +33(4)72431323; e-Mail: medebiel@univ-lyon1.fr;
^b Department of Chemical Science and Engineering, Faculty of Engineering, Kobe University, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan

Abstract

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Abstract

Indium can efficiently mediate the Reformatsky-type reaction between some β-aminovinyl chlorodifluoromethyl ketones and a series of heteroaryl aldehydes, to afford the corresponding difluoromethylene compounds in good to high yields.

Key words

indium - Reformatsky - fluorine - β-aminovinyl ketones - nucleophilic additions

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References

1 Tozer MJ. Herpin T. Tetrahedron 1996, 52: 8619

2 Médebielle M. Keyrouz R. Langlois B. Billard T. Dolbier WR. Burkholder C. Ait-Mohand S. Okada E. Ashida T. In Electron Transfer Reactions in Organic Synthesis Vanelle P. Research Signpost; Trivandrum: 2002. p.89

3a Billard T. Langlois BR. Médebielle M. Tetrahedron Lett. 2001, 42: 3463

3b Médebielle M. Keirouz R. Okada E. Ashida T. Synlett 2001, 821

3c Burkholder C. Dolbier WRJr. Médebielle M. Ait-Mohand S. Tetrahedron Lett. 2001, 42: 3459

3d Dolbier WR. Médebielle M. Ait-Mohand S. Tetrahedron Lett. 2001, 42: 4811

3e Burkholder C. Dolbier WR. Médebielle M. J. Org. Chem. 1998, 63: 5385

4a Tommasino J.-B. Brondex A. Médebielle M. Thomalla M. Langlois BR. Billard T. Synlett 2002, 1697

4b Hapiot P. Médebielle M. J. Fluorine Chem. 2001, 107: 285

4c Fujii S. Kato K. Médebielle M. Tetrahedron 2000, 56: 2655

4d Burkholder C. Dolbier WR. Médebielle M. J. Fluorine Chem. 2000, 102: 369

4e Médebielle M. Tetrahedron Lett. 1995, 36: 2071

5 Burkholder C. Dolbier WR. Médebielle M. J. Fluorine Chem. 2000, 102: 369

6For a review see:

6 Nenajdenko VG. Sanin AV. Balenkova ES. Russ. Chem. Rev. (Engl. Trans.) 1999, 68: 437

Selected references:

7a Bonacorso HG. Duarte SHG. Zanatta N. Martins MA. Synthesis 2002, 1037

7b Kruchok IS. Gerus II. Kukhar VP. Synthesis 2002, 71

7c Krasovsky AL. Nenajdenko VG. Balenkova ES. Tetrahedron 2001, 57: 201

7d Baraznenok IL. Nenajdenko VG. Balenkova ES. Eur. J. Org. Chem. 1999, 937

7e Okada E. Kinomura T. Higashiyama Y. Heterocycles 1998, 48: 2347

7f Okada E. Kinomura T. Higashiyama Y. Takeuchi H. Hojo M. Heterocycles 1997, 46: 129

7g Okada E. Kinomura T. Takeuchi H. Hojo M. Heterocycles 1997, 44: 349

7h Okada E. Masuda R. Hojo M. Inoue R. Synthesis 1992, 533

7i Hojo M. Masuda R. Okada E. Mochizuki Y. Synthesis 1992, 455

7j Okada E. Masuda R. Hojo M. Yoshida R. Heterocycles 1992, 34: 1435

7k Okada E. Masuda R. Hojo M. Heterocycles 1992, 34: 1927

7l Okada E. Masuda R. Hojo M. Heterocycles 1992, 34: 791

7m Hojo M. Masuda R. Okada E. Yamamoto H. Morimoto K. Okada K. Synthesis 1990, 195

7n Hojo M. Masuda R. Okada E. Chem. Lett. 1990, 2095

7o Hojo M. Masuda R. Okada E. Tetrahedron Lett. 1989, 30: 6173

7p Hojo M. Masuda R. Okada E. Synthesis 1986, 1013

8 Lang RW. Schaub B. Tetrahedron Lett. 1988, 29: 2943

9 Amii H. Kobayashi T. Terasawa H. Uneyama K. Org. Lett. 2001, 3: 3103

It is known that TDAE and their cyclic analogues could act as electron-donors and good nucleophiles. See:

10a Wiberg N. Angew. Chem. 1968, 20: 869

10b Lemal DM. In The Chemistry of the Amino Group Chap. 12: Patai S. Wiley Interscience; New York: 1968. p.701-748

10c Wanzlick H.-W. Kleiner H.-J. Chem. Ber. 1963, 96: 3024

11a Chaussard J. Folest J.-C. Nédélec J. Périchon J. Sibille S. Troupel M. Synthesis 1990, 369

11b We still need to check if the coupling reactions of 2a, 2b, 3a, and 4a with benzaldehyde could be achieved using another soluble anode such as Mg. Indeed for some reported examples in the literature choice of the sacrificial anode play a crucial role; see for example: Rajaonah M. Rock MH. Bégué J.-P. Bonnet-Delpon D. Condon S. Nédélec J.-Y. Tetrahedron Lett. 1998, 39: 3137

12 Chung WJ. Higashiya H. Welch JT. J. Fluorine Chem. 2001, 112: 343

Reviews:

13a Ranu BC. Eur. J. Org. Chem. 2000, 2347

13b Li C.-J. Chan T.-H. Tetrahedron 1999, 55: 11149

14a Chung WJ. Higashiya S. Welch JT. Tetrahedron Lett. 2002, 43: 5801

14b Lan Y. Hammond GB. Org. Lett. 2002, 4: 2437

14c Shen Q. Hammond GB. Org. Lett. 2001, 3: 2213

14d Wang Z. Hammond GB. J. Org. Chem. 2000, 65: 6547

14e Kirihara M. Takuwa T. Takizawa S. Momose T. Nemoto H. Tetrahedron 2000, 56: 8275

14f Percy JM. Pintat S. Chem. Commun. 2000, 607

14g Loh T.-P. Li X.-R. Tetrahedron 1999, 55: 5611

14h Loh T.-P. Li X.-R. Eur. J. Org. Chem. 1999, 1893

14i Loh T.-P. Zhou J.-R. Li X.-R. Tetrahedron Lett. 1999, 40: 9333

14j Loh T.-P. Li X.-R. Tetrahedron Lett. 1997, 38: 869

Indium-Mediated Reformatsky-Type Reaction of β-Aminovinyl Chlorodifluoro­methyl Ketones with Heteroaryl Aldehydes

Indium-Mediated Reformatsky-Type Reaction of β-Aminovinyl Chlorodifluoromethyl Ketones with Heteroaryl Aldehydes