Highly Diastereoselective Synthesis of β-Hydroxy Amides from β-Keto Amides

Giuseppe Bartoli; Marcella Bosco; Enrico Marcantoni; Massimo Massaccesi; Samuele Rinaldi; Letizia Sambri

doi:10.1055/s-2004-829192

PSP

Highly Diastereoselective Synthesis of β-Hydroxy Amides from β-Keto Amides

Giuseppe Bartoli*^a, Marcella Bosco^a, Enrico Marcantoni^b, Massimo Massaccesi^a, Samuele Rinaldi^c, Letizia Sambri^a
^a Dipartimento di Chimica Organica ‘A. Mangini’, v. le Risorgimento 4, 40136 Bologna, Italy
Fax: +39(51)2093654; e-Mail: giuseppe.bartoli@unibo.it;
^b Dipartimento di Scienze Chimiche, Università di Camerino, v. S. Agostino 1, 62032 Camerino (MC), Italy
^c Dipartimento di Scienze e Materiali della Terra, Università di Ancona, v. Brecce Bianche, 60131 Ancona, Italy

Abstract

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Abstract

β-Hydroxy amides with stereodefined geometry represent an important unit present in various natural products. The diastereoselective preparation of amides carrying a secondary or tertiary alcohol in β-position is described here.

Key words

diastereoselectivity - hydroxy amides - TiCl₄ - organocerium reagents - boranes

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References

<A NAME="RZ10804SS-1">1</A> Jacobson IC. Reddy PG. Wasserman ZR. Hardman KD. Covington MB. Arner EC. Copeland RA. Decicco CP. Magolda R. Bioorg. Med. Chem. Lett. 1998, 8: 837

<A NAME="RZ10804SS-2">2</A> Kakei H. Nemoto T. Ohshima T. Shibasaki M. Angew. Chem. Int. Ed. 2004, 43: 317

<A NAME="RZ10804SS-3A">3a</A> Heathcock CH. In Asymmetric Synthesis Vol. 3: Morrison JD. Academic Press; New York: 1984. p.111

<A NAME="RZ10804SS-3B">3b</A> Evans DA. Nelson JV. Taber TR. Top. Stereochem. 1984, 13: 1

<A NAME="RZ10804SS-3C">3c</A> Evans DA. McGee LR. Tetrahedron Lett. 1980, 21: 3975

<A NAME="RZ10804SS-3D">3d</A> Goasdoue C. Goasdoue N. Gaudemar M. J. Organomet. Chem. 1981, 208: 279

<A NAME="RZ10804SS-3E">3e</A> Canceill J. Jacques J. Bull. Soc. Chim. Fr. 1970, 2180

<A NAME="RZ10804SS-3F">3f</A> Kamimura A. Omata Y. Mitsudera H. Kakehi A. J. Chem. Soc., Perkin Trans. 1 2000, 4499

<A NAME="RZ10804SS-4A">4a</A> Taniguchi M. Fujii H. Oshima K. Utimoto K. Bull. Chem. Soc. Jpn. 1994, 67: 2514

<A NAME="RZ10804SS-4B">4b</A> Molander GA. Andrews SW. Tetrahedron Lett. 1986, 27: 3115

<A NAME="RZ10804SS-4C">4c</A> Molander GA. Etter JB. Zinke PW. J. Am. Chem. Soc. 1987, 109: 453

<A NAME="RZ10804SS-5A">5a</A> Taniguchi M. Fujii H. Oshima K. Utimoto K. Tetrahedron 1993, 49: 11169

<A NAME="RZ10804SS-5B">5b</A> Fujita M. Hiyama T. J. Am. Chem. Soc. 1985, 107: 8294

<A NAME="RZ10804SS-5C">5c</A> Fujita M. Hiyama T. J. Org. Chem. 1988, 53: 5405

<A NAME="RZ10804SS-5D">5d</A> Fujita M. Hiyama T. J. Org. Chem. 1988, 53: 5415

<A NAME="RZ10804SS-5E">5e</A> Fujita M. Hiyama T. Org. Synth. 1990, 69: 44

<A NAME="RZ10804SS-5F">5f</A> Fujii H. Oshima K. Utimoto K. Tetrahedron Lett. 1991, 32: 6147

<A NAME="RZ10804SS-6">6</A> Mengel A. Reiser O. Chem. Rev. 1999, 99: 1191

<A NAME="RZ10804SS-7">7</A> Bartoli G. Bosco M. Dalpozzo R. Marcantoni E. Sambri L. Chem.-Eur. J. 1997, 3: 1941

<A NAME="RZ10804SS-8">8</A> Bartoli G. Bosco M. Di Martino E. Marcantoni E. Sambri L. Eur. J. Org. Chem. 2001, 2901

<A NAME="RZ10804SS-9">9</A> The proton abstraction in 4A is expected to be difficult due to stereoelectronic factors (H in pseudo equatorial position): Deslongchamps P. In Stereoelectronic Effects in Organic Chemistry Vol. 1: Pergamon; New York: 1983. p.274

<A NAME="RZ10804SS-10">10</A> Bartoli G. Marcantoni E. Sambri L. In Seminars in Organic Synthesis: XXV Summer School ‘A. Corbella’ 12-16/6/2000, Gargnano Società Chimica Italiana; Camerino: 2000. p.117-138

<A NAME="RZ10804SS-11A">11a</A> Imamoto T. Lanthanides in Organic Synthesis Academic Press; New York: 1994. p.68

<A NAME="RZ10804SS-11B">11b</A> Imamoto T. In Comprehensive Organic Synthesis Vol. 1: Trost BM. Fleming I. Schreiber SL. Pergamon; London: 1991. Chap. 1.8.

<A NAME="RZ10804SS-12">12</A> Bartoli G. Bosco M. Marcantoni E. Massaccesi M. Rinaldi S. Sambri L. Tetrahedron Lett. 2001, 42: 6093

<A NAME="RZ10804SS-13">13</A> Bartoli G. Bellucci MC. Bosco M. Marcantoni E. Sambri L. Chem.-Eur. J. 1998, 4: 2154

<A NAME="RZ10804SS-14">14</A> Cooper GD. Finkbeiner HL. J. Org. Chem. 1962, 27: 1493

<A NAME="RZ10804SS-15">15</A> Reetz MT. Organometallics in Synthesis, A Manual Schlosser M. 1994. p.195

<A NAME="RZ10804SS-16">16</A> Bartoli G. Bosco M. Marcantoni E. Massaccesi M. Rinaldi S. Sambri L. Tetrahedron Lett. 2001, 42: 8811

This procedure can be successfully applied, with slight modifications (the use of BH₃·py complex instead of BH₃·Me₂S) to closely related systems.

<A NAME="RZ10804SS-17B">17b</A> For the reduction of β-keto sulfones, see: Bartoli G. Bosco M. Cingolani S. Marcantoni E. Sambri L. J. Org. Chem. 1998, 63: 3624

<A NAME="RZ10804SS-17C">17c</A> For the reduction of β-keto esters, see: Bartoli G. Bellucci MC. Alessandrini S. Malavolta M. Marcantoni E. Sambri L. Dalpozzo R. J. Org. Chem. 1999, 64: 1986

<A NAME="RZ10804SS-17D">17d</A> For the reduction of α-nitroketones, see: Ballini R. Bosica G. Marcantoni E. Vita P. Bartoli G. J. Org. Chem. 2000, 65: 5854

<A NAME="RZ10804SS-17E">17e</A> For the reduction of β-keto carbonitriles, see: Bartoli G. Bosco M. Dalpozzo R. De Nino A. Procopio A. Sambri L. Tagarelli A. Eur. J. Org. Chem. 2001, 2971