A Concise and Efficient Stereoselective Synthesis of the C1-C11 Fragment of Macrolactin A

Carlo Bonini; Lucia Chiummiento; Valeria Videtta; Françoise Colobert; Guy Solladié

doi:10.1055/s-2006-950424

LETTER

A Concise and Efficient Stereoselective Synthesis of the C1-C11 Fragment of Macrolactin A

Carlo Bonini*^a, Lucia Chiummiento^a, Valeria Videtta^a, Françoise Colobert^b, Guy Solladié^b
^a Dipartimento di Chimica, Università degli Studi della Basilicata, via N. Sauro 85, 85100 Potenza, Italy
Fax: +39(971)202223; e-Mail: bonini@unibas.it;
^b Laboratoire de Stéréochemie associé au CNRS, Université Louis Pasteur (ECPM), rue Bacquerel, 67087 Strasbourg, France

Abstract

All articles of this category

Abstract

A stereoselective synthesis of the C1-C11 fragment of macrolactin A, using original approaches for the introduction of the Z,E-diene stereochemistry and the C-7 stereogenic center, is reported. The adopted strategy has allowed us to build up the fragment by the assembly of three key intermediates via cross-metathesis, Still-Gennari, and Wittig olefinations. Opening of the commercially available chiral benzyl glycidol epoxide to the corresponding homoallylic alcohol introduced the C-7 chiral center. A cross-metathesis reaction was used to create the C5-C4 E double bond. The Still-Gennari reaction introduced the 2Z,4E-diene moiety and finally the Wittig reaction with a propargylic triphenylphosphorane introduced directly the 1,3-enyne unit in a highly efficient stereoselective fashion.

Key words

macrolactin A - cross-metathesis - Still-Gennari reaction - Wittig olefination - dienes

Full Text

References

References and Notes

<A NAME="RG22206ST-1">1</A> Gustafson K. Roman M. Fenical W. J. Am. Chem. Soc. 1989, 111: 7519

<A NAME="RG22206ST-2A">2a</A> Kim H.-H. Kim W.-G. Ryoo I.-J. Kim C.-J. Suk J.-E. Han K.-H. Hwang S.-Y. Yoo I.-D. J. Microbiol. Biotechnol. 1997, 7: 429

<A NAME="RG22206ST-2B">2b</A> Jaruchoktaweechai C. Suwanborirus K. Tanasupawatt S. Kittakoop P. Menasveta P. J. Nat. Prod. 2000, 63: 984

<A NAME="RG22206ST-2C">2c</A> Nagao T. Adachi K. Sakai M. Nishijima M. Sano H. J. Antibiot. 2001, 54: 333

<A NAME="RG22206ST-2D">2d</A> Romero-Tabarez M. Jansen R. Sylla M. Lünsdorf H. Häußler S. Santosa DA. Timmis KN. Molinari G. Antimicrob Agents Chemother. 2006, 50: 1701

For the total synthesis, see:

<A NAME="RG22206ST-3A">3a</A> Smith AB. Ott GR. J. Am. Chem. Soc. 1996, 118: 13095

<A NAME="RG22206ST-3B">3b</A> Kim Y. Singer RA. Carreira EM. Angew. Chem. Int. Ed. 1998, 37: 1261

<A NAME="RG22206ST-3C">3c</A> Marino JP. McClure MS. Holub DP. Comasseto JV. Tucci FC. J. Am. Chem. Soc. 2001, 124: 1664

For partial syntheses, see:

<A NAME="RG22206ST-4A">4a</A> Benvegnu T. Schio L. Le Floch Y. Grèe R. Synlett 1994, 505

<A NAME="RG22206ST-4B">4b</A> Donaldson WA. Bell PT. Wang Z. Bennett DW. Tetrahedron Lett. 1994, 35: 5829

<A NAME="RG22206ST-4C">4c</A> Boyce RJ. Pattenden G. Tetrahedron Lett. 1996, 37: 3501

<A NAME="RG22206ST-4D">4d</A> Benvegnu T. Toupet L. Greè R. Tetrahedron 1996, 52: 11811

<A NAME="RG22206ST-4E">4e</A> Benvegnu T. Greè R. Tetrahedron 1996, 52: 11821

<A NAME="RG22206ST-4F">4f</A> Prahlad V. Donaldson WA. Tetrahedron Lett. 1996, 37: 9169

<A NAME="RG22206ST-4G">4g</A> Gonzàlez A. Aiguadè J. Urp F. Villarasa J. Tetrahedron Lett. 1996, 37: 8949

<A NAME="RG22206ST-4H">4h</A> Tanimori S. Morita Y. Tsubota M. Nakayama M. Synth. Commun. 1996, 26: 559

<A NAME="RG22206ST-4I">4i</A> Donaldason WA. Barmann H. Prahlad V. Tao C. Yun YK. Wang Z. Tetrahedron 2000, 56: 2283

<A NAME="RG22206ST-4J">4j</A> Li S. Xu R. Bai D. Tetrahedron Lett. 2000, 41: 3463

<A NAME="RG22206ST-4K">4k</A> Hoffmann HMR. Vakalopoulos A. Org. Lett. 2001, 3: 177

<A NAME="RG22206ST-4L">4l</A> Shukun L. Donaldson WA. Synthesis 2003, 13: 2064

<A NAME="RG22206ST-4M">4m</A> Fukuda A. Kobayashi Y. Kimachi T. Takemoto Y. Tetrahedron 2003, 59: 9305

<A NAME="RG22206ST-4N">4n</A> Li S. Xiao X. Yan X. Xu R. Bai D. Tetrahedron 2005, 61: 11291

For a total synthesis of an analogue of macrolactin A, see:

<A NAME="RG22206ST-4O">4o</A> Kobayashi Y. Fukuda A. Kimachi T. Ju-ichi M. Takemoto Y. Tetrahedron Lett. 2004, 45: 677

<A NAME="RG22206ST-4P">4p</A> Kobayashi Y. Fukuda A. Kimachi T. Ju-ichi M. Takemoto Y. Tetrahedron 2005, 61: 2607

<A NAME="RG22206ST-5">5</A> Bonini C. Chiummiento L. Pullez M. Solladié G. Colobert F. J. Org. Chem. 2004, 69: 5015

<A NAME="RG22206ST-6">6</A> Extensive work on different propargylic alcohols led to a general protocol for the preparation of aromatic and heteroaromatic sulfones as reported in: Bonini C. Chiummiento L. Videtta V. Synlett 2005, 3067

<A NAME="RG22206ST-7A">7a</A> Blakemore PR. J. Chem. Soc., Perkin Trans. 1 2002, 2563

<A NAME="RG22206ST-7B">7b</A> Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr. 1993, 130: 336

<A NAME="RG22206ST-7C">7c</A> Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr. 1993, 130: 856

<A NAME="RG22206ST-7D">7d</A> Baudin JB. Hareau G. Julia SA. Ruel O. Tetrahedron Lett. 1991, 32: 1175

The stereochemical outcome of the one-pot Julia olefination is generally substrate (sulfone and aldehyde) controlled. Moreover, there are some examples where β,γ-unsaturated BT-sulfones give high levels of E stereoselectivity (see ref. 7a).

<A NAME="RG22206ST-9">9</A> Bonini C. Chiummiento L. Lopardo MT. Pullez M. Colobert F. Solladié G. Tetrahedron Lett. 2003, 44: 2695

For recent reviews of the alkene metathesis reaction, see:

<A NAME="RG22206ST-10A">10a</A> Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed. 2005, 44: 4490

<A NAME="RG22206ST-10B">10b</A> Schmidt B. Hermanns J. Top. Organomet. Chem. 2004, 7: 223

<A NAME="RG22206ST-10C">10c</A> Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012

<A NAME="RG22206ST-10D">10d</A> Grubbs RH. Chang S. Tetrahedron 1998, 54: 4413

<A NAME="RG22206ST-11">11</A> These high Z selectivities prompted us to study the one-pot Julia olefination with propargylic sulfone 6 and several different aromatic and aliphatic aldehydes more extensively: Bonini C. Chiummiento L. Videtta V. Synlett 2006, 2079

<A NAME="RG22206ST-12A">12a</A> Still WC. Gennari C. Tetrahedron Lett. 1983, 24: 4405

<A NAME="RG22206ST-12B">12b</A> Yu W. Su M. Tetrahedron Lett. 1999, 40: 6725

Attempts were made to prepare the tributyl propargylic phosphorane but we had some problems obtaining it pure.

Compound 3 : R _f 0.26 (PE-Et₂O-CH₂Cl₂, 99:2:1). ¹H NMR (500 MHz, CDCl₃): δ = 7.40 (dd, J _4,5 = 14.4 Hz, J _4,3 = 11.9 Hz, 1 H), 6.55 (t, J _3,2 = J _3,4 = 11.0 Hz, 1 H), 6.18 (dd, J _8,9 = 16.0 Hz, J _8,7 = 5.0 Hz, 1 H), 6.03 (dt, J _5,4 = 15.5 Hz, J _5,6 = 8.0 Hz, 1 H), 5.72 (d, J _9,8 = 16.0 Hz, 1 H), 5.61 (d, J _2,3 = 11.5 Hz, 1 H), 4.26 (m, 1 H), 3.73 (s, 3 H), 2.41 (m, 2 H), 0.89 (s, 9 H), 0.19 (s, 9 H), 0.03 (s, 6 H). ¹³C NMR (125 MHz, CDCl₃): δ = 166.9, 146.4, 145.0, 140.4, 129.2, 115.8, 109.2, 103.3, 95.0, 71.8, 51.1, 41.3, 25.8, 18.1, -0.1, -4.6, -4.9. EI-MS: m/z (%) = 392 (100), 267 (100), 73 (50), 75 (20), 45. Anal. Calcd for C₂₁H₃₆O₃Si₂: C, 64.23; H, 9.24. Found: C, 64.32; H, 9.18.