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Synlett 2002(8): 1261-1264
DOI: 10.1055/s-2002-32968
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantioselective Taxanes Approach Using Both Enantiomers of the Same Building-Block. Part 1: Taxol® A-Ring Subunit

Gérard Audran, Jean-Pierre Uttaro, Honoré Monti*
Laboratoire de Réactivité Organique Sélective UMR 6516 Faculté des Sciences de St-Jérôme (case 551), Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Fax: +33(4)91288862; e-Mail: honore.monti@univ.u-3mrs.fr;
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Publication History

Received 14 May 2002
Publication Date:
25 July 2002 (online)

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Abstract

An efficient enantioselective synthesis of fully-oxygenated Taxol® A-ring subunit has been achieved using (-)-karahana lactone, (-)-2, as an enantiopure starting building-block and a diastereoselective allylic hydroxylation as the key step.

Key words

stereoselectivity - enantioselective synthesis - Taxol® - antitumor agents

    References

  • 1a McGuire WP. Rowinsky EK. Rosenshein NB. Grumbine FC. Ettinger DS. Armstrong DK. Donehower RC. Ann. Inter. Med.  1989,  III:  273 
    Google Scholar
  • 1b Rowinsky EK. Cazenave LA. Donehower RC. Natl. Cancer Inst.  1990,  82:  1247 
    Google Scholar
  • 1c Suffness M. Ann. Rep. Med. Chem.  1993,  28:  305 
    Google Scholar
  • 1d Holmes FA. Kudelka AP. Kavanagh JJ. Huber MH. Ajani JA. Valero V. In Taxane Anticancer Agents: Basic Science and Current Status   Georg GI. Chen TT. Ojima I. Vyas DM. ACS Symposium Series 583, American Chemical Society; Washington D.C.: 1995.  p.31 
    Google Scholar
  • 1e Arbuck SG. Blaylock BA. In Taxol: Science and Applications   Suffness M. CRC Press; Boca Raton: 1995.  p.379 
    Google Scholar
  • 1f Rowinsky EK. Donehower RC. Eng. J. Med.  1995,  332:  1004 
    Google Scholar
  • 2 Wani MC. Taylor HL. Wall ME. Coggon P. McPhail AT. J. Am. Chem. Soc.  1971,  93:  2325 
    CrossrefPubMedGoogle Scholar
  • 3a Guéritte-Voegelein F. Guénard D. Lavelle F. Le Goff M.-T. Potier P. J. Med. Chem.  1991,  34:  992 
    Google Scholar
  • 3b Guénard D. Guéritte-Voegelein F. Potier P. Acc. Chem. Res.  1993,  26:  160 
    Google Scholar
  • 3c Potier P. C. R. Acad. Agric. Fr.  2000,  86:  179 
    Google Scholar
  • 4a Nicolaou KC. Yang Z. Liu JJ. Ueno H. Nantermet PG. Guy RK. Claiborne CF. Renaud J. Couladouros EA. Paulvannan K. Sorensen EJ. Nature (London)  1994,  367:  630 
    CrossrefGoogle Scholar
  • 4b Nicolaou KC. Ueno H. Liu J.-J. Nantermet PG. Yang Z. Renaud J. Paulvannan K. Chadha R. J. Am. Chem. Soc.  1995,  117:  653 ; and references cited
    CrossrefGoogle Scholar
  • 4c Masters JJ. Link JT. Snyder LB. Young WB. Danishefsky SJ. Angew. Chem., Int. Ed. Engl.  1995,  34:  1723 
    CrossrefGoogle Scholar
  • 4d Danishefsky SJ. Masters JJ. Young WB. Link JT. Snyders LB. Magee TV. Jung DK. Isaacs RCA. Bornmann WG. Alaimo CA. Coburn CA. Di Grandi MJ. J. Am. Chem. Soc.  1996,  118:  2843 
    CrossrefGoogle Scholar
  • 4e Holton RA. Somoza C. Kim H.-B. Liang F. Biediger RJ. Boatman PD. Shindo M. Smith CC. Kim S. Nadizadeh H. Suzuki Y. Tao C. Vu P. Tang S. Zhang P. Murthi KK. Gentile LN. Liu JH. J. Am. Chem. Soc.  1994,  116:  1597 
    CrossrefGoogle Scholar
  • 4f Holton RA. Somoza C. Kim H.-B. Liang F. Biediger RJ. Boatman PD. Shindo M. Smith CC. Kim S. Nadizadeh H. Suzuki Y. Tao C. Vu P. Tang S. Zhang P. Murthi KK. Gentile LN. Liu JH. J. Am. Chem. Soc.  1994,  116:  1599 
    CrossrefGoogle Scholar
  • 4g Wender PA. Badham NF. Conway SP. Floreancig PE. Glass TE. Houze JB. Crauss NE. Lee D. Marquess DG. McGrane PL. Meng W. Natchus MG. Shuker AJ. Sutton JC. Taylor RE. J. Am. Chem. Soc.  1997,  119:  2757 ; and references cited
    CrossrefGoogle Scholar
  • 4h Mukaiyama T. Chiina I. Iwadare H. Saitoh M. Nishimura T. Ohkawa N. Sakoh H. Nishimura K. Tani Y.-i. Hasegawa M. Yamada K. Saitoh K. Chem.-Eur. J.  1999,  5:  121 
    CrossrefGoogle Scholar
  • 4i Morihira K. Hara R. Kawahara S. Nishimori T. Nakamura N. Kusama H. Kuwajima I. J. Am. Chem. Soc.  1998,  120:  12980 
    CrossrefGoogle Scholar
  • 4j Kusama H. Hara R. Kawahara S. Nishimori T. Kashima H. Nakamura N. Morihira K. Kuwajima I. J. Am. Chem. Soc.  2000,  122:  3811 
    CrossrefGoogle Scholar
  • Some recent publications and references therein:
  • 5a Yuan H. Kingston DGI. Tetrahedron  1999,  55:  9089 
    Google Scholar
  • 5b Ojima I. Bounaud PY. Ahern DG. Bioorg. Med. Chem. Lett.  1999,  9:  1189 
    Google Scholar
  • 5c Wittman MD. Alstadt TJ. Kadow JF. Vyas DM. Johnson K. Farichild C. Long B. Tetrahedron Lett.  1999,  40:  4943 
    Google Scholar
  • 5d Gunatilaka AAL. Ramdayal FD. Sarragiotto MH. Kingston DGI. Sackett DL. Hamel E. J. Org. Chem.  1999,  64:  2694 
    Google Scholar
  • 5e Zeng Q. Paquette LA. Synlett  1999,  1547 
    Google Scholar
  • 5f Wenz M. Grosbach D. Beitzel M. Blechert S. Synthesis  1999,  607 
    Google Scholar
  • 5g Wei C.-Q. Zhao G. Jian X.-R. Ding Y. J. Chem. Soc., Perkin Trans. 1  1999,  3531 
    Google Scholar
  • 5h Magnus P. Westwood N. Spyvee M. Frost C. Linnane P. Tavares F. Lynch V. Tetrahedron  1999,  55:  6435 
    Google Scholar
  • 5i Arseniyadis S. del Rosario Rico Ferreira M. Quilez de Moral J. Martin Hernando JI. Birlirakis N. Potier P. Tetrahedron: Asymmetry  1999,  10:  193 
    Google Scholar
  • 5j Bourgeois D. Lallemand J.-Y. Pancrazi A. Prunet J. Synlett  1999,  1555 
    Google Scholar
  • 5k Cheng Q. Oritani T. Horiguchi T. Tetrahedron  2000,  56:  1667 
    Google Scholar
  • 5l Momose T. Setoguchi M. Fujita T. Tamura H. Chida N. Chem. Commun.  2000,  2237 
    Google Scholar
  • 5m Bourgeois D. Prunet J. Pancrazi A. Prange T. Lallemand J.-Y. Eur. J. Org. Chem.  2000,  4029 
    Google Scholar
  • 5n del Rosario Rico Ferreira M. Martin Hernando JI. CandelaLena JI. Birlirakis N. Arseniyadis S. Synlett  2000,  113 
    Google Scholar
  • 5o Martin Hernando JI. del Rosario Rico Ferreira M. CandelaLena JI. Birlirakis N. Arseniyadis S. Tetrahedron: Asymmetry  2000,  11:  951 
    Google Scholar
  • 5p Merckle L. Dubois J. Place E. Thoret S. Guéritte F. Guerard D. Poupat C. Ahond A. Potier P. J. Org. Chem.  2001,  66:  5058 
    Google Scholar
  • 5q Miyamoto S. Doi T. Takahashi T. Synlett  2002,  97 
    Google Scholar
  • 6 Galano J.-M. Audran G. Monti H. Tetrahedron  2000,  56:  7477 
    CrossrefGoogle Scholar
  • 7 Uttaro J.-P. Audran G. Galano J.-M. Monti H. Tetrahedron Lett.  2002,  43:  2757 
    CrossrefGoogle Scholar
  • Syntheses of A-ring units and references therein:
  • 8a Törmäkangas OP. Toivola RJ. Karvinen EK. Koskinen AMP. Tetrahedron  2002,  58:  2175 
    CrossrefGoogle Scholar
  • 8b Carballares S. Craig D. Lane CAL. MacKenzie AR. Mitchell WP. Wood A. Chem. Commun.  2000,  1767 
    CrossrefGoogle Scholar
  • 8c Bourgeois D. Maiti G. Pancrazi A. Prunet J. Synlett  2000,  323 
    CrossrefGoogle Scholar
  • 8d Nivlet A. Dechoux L. Martel J.-P. Proess G. Mannes D. Alcaraz L. Harnett JJ. Le Gall T. Mioskowski C. Eur. J. Org. Chem.  1999,  3241 
    CrossrefGoogle Scholar
  • 8e Wei C.-Q. Jiang X.-R. Ding Y. Tetrahedron  1998,  54:  12623 
    CrossrefGoogle Scholar
  • 8f Ishikawa T. Ikeda S. Ibe M. Saito S. Tetrahedron  1998,  54:  5869 
    CrossrefGoogle Scholar
  • 8g Stork G. Doi K. Liu L. Tetrahedron Lett.  1997,  38:  7471 
    CrossrefGoogle Scholar
  • 8h Yadav JS. Srinivas D. Tetrahedron Lett.  1997,  38:  7789 
    CrossrefGoogle Scholar
  • 8i Crich D. Natarajan S. Crich JZ. Tetrahedron  1997,  53:  7139 
    CrossrefGoogle Scholar
  • 8j Wennerberg J. Polla M. Frejd T. J. Org. Chem.  1997,  62:  8735 
    CrossrefGoogle Scholar
  • 8k Funk RL. Yost KJ. J. Org. Chem.  1996,  61:  2598 
    CrossrefGoogle Scholar
  • 8l Frost C. Linnane P. Magnus P. Spyvee M. Tetrahedron Lett.  1996,  37:  9139 
    CrossrefGoogle Scholar
  • 8m Toivola RJ. Koskinen AMP. Synlett  1996,  1159 
    CrossrefGoogle Scholar
  • 8n Kishi Y. Kress MH. Tetrahedron Lett.  1995,  36:  4583 
    CrossrefGoogle Scholar
  • 8o Tjepkema MW. Wilson PD. Wong T. Romero MA. Audrain H. Fallis AG. Tetrahedron Lett.  1995,  36:  6039 
    CrossrefGoogle Scholar
  • 8p Wender PA. Wessjohann LA. Peschke B. Rawlins DB. Tetrahedron Lett.  1995,  36:  7181 
    CrossrefGoogle Scholar
  • 8q Taber DF. Sahli A. Yu H. Meagley RP. J. Org. Chem.  1995,  60:  6571 
    CrossrefGoogle Scholar
  • 8r Karvinen EK. Koskinen AMP. Tetrahedron  1995,  51:  7555 
    CrossrefGoogle Scholar
  • Ermolenko MS. Shekharam T. Lukacs G. Potier P. Tetrahedron Lett.  1995,  36:  2461 
    CrossrefGoogle Scholar
  • 8t Winkler JD. Bhattacharya SK. Liotta F. Batey RA. Heffernan GD. Cladingboel DE. Kelly RC. Tetrahedron Lett.  1995,  36:  2211 
    CrossrefGoogle Scholar
  • 8u Nicolaou KC. Liu J.-J. Ueno H. Sorensen EJ. Claiborne CF. Guy RK. Hwang C.-K. Nakada M. Nantermet PG. J. Am. Chem. Soc.  1995,  117:  634 
    CrossrefGoogle Scholar
  • 8v Doi T. Robertson J. Stork G. Yamashita A. Tetrahedron Lett.  1994,  35:  1481 
    CrossrefGoogle Scholar
  • 8w Nakamura T. Waizumi N. Horiguchi Y. Kuwajima I. Tetrahedron Lett.  1994,  35:  7813 
    CrossrefGoogle Scholar
  • 8x Di Grandi MJ. Jung DK. Krol WJ. Danishefsky SJ. J. Org. Chem.  1993,  58:  4989 
    CrossrefGoogle Scholar
  • 8y Arseniyadis S. Yashunsky DV. Pereira de Freitas R. Muñoz Dorado M. Toromanoff E. Potier P. Tetrahedron Lett.  1993,  34:  1137 
    CrossrefGoogle Scholar
  • 8z Polla M. Frejd T. Tetrahedron  1993,  49:  2701 
    CrossrefGoogle Scholar
  • Syntheses of A-ring units and references therein:
  • 9a Kress MH. Ruel R. Miller WH. Kishi Y. Tetrahedron Lett.  1993,  34:  5999 
    Google Scholar
  • 9b Queneau Y. Krol WJ. Bornmann WG. Danishefsky SJ. J. Org. Chem.  1992,  57:  4043 
    Google Scholar
  • 9c Nicolaou KC. Hwang C.-K. Sorensen EJ. Clairborne CF. J. Chem. Soc., Chem. Commun.  1992,  1117 
    Google Scholar
  • 9d Bonnert RV. Jenkins PR. J. Chem. Soc., Perkin Trans. 1  1989,  413 
    Google Scholar
  • 9e Lin J. Nikaido MM. Clark GJ. J. Org. Chem.  1987,  52:  3745 
    Google Scholar
10

Preparation of (-)-3. To a stirred solution of karahana lactone (-)-2 [6] (400 mg, 2.41 mmol) in dry CH2Cl2 (40 mL) was added selenium dioxide (107 mg, 0.96 mmol), tert-butyl hydroperoxide (70 wt% in water, 868 mg, 9.64 mmol) and a catalytic amount of salicylic acid under an argon atmosphere. The reaction mixture was heated to reflux for 3 d, cooled to r.t. and Na2SO3 (2.5 g, 20 mmol) and 1 mL of water were added. The mixture was stirred for a further 30 min, filtered through a pad of MgSO4 and concentrated. After purification by crystallization from Et2O-hexane, 354 mg of pure alcohol (-)-3 were obtained as white crystals (rdt 85%).

11

Spectroscopic data of compounds (-)-3 and (-)-1: (-)-3: mp 155 °C, [α]D 25 -142.9 (c 1.0, CHCl3). IR (KBr): 3440, 3091, 1759, 1036, 905 cm-1. 1H NMR (500 MHz, CDCl3): δ = 5.18 (s, 1 H, H-9), 5.08 (s, 1 H, H-9), 4.42 (d, J = 6.1 Hz, 1 H, H-3), 4.36 (br. d, J = 3.7 Hz, 1 H, H-5), 2.77 (s, 1 H, H-1), 2.22 (dd, J = 15.7, 3.8 Hz, 1 H, Hα-4), 2.08 (ddd, J = 15.7, 6.1, 1.5 Hz, 1 H, Hβ-4), 1.21 (s, 3 H, CH3 β), 0.95 (s, 3 H, CH3 α).
13C NMR (125 MHz, CDCl3): δ = 176.6 (C-7), 143.9 (C-2), 117.0 (CH2-9), 84.3 (CH-5), 68.0 (CH-3), 56.6 (CH-1), 42.8 (C-8), 32.6 (CH2-4), 25.3 (CH3 ), 20.1 (CH3 ). Anal. Calcd for C10H14O3: C, 65.92; H, 7.74. Found: C, 65.64; H 7.72.
(-)-1: Mp 59 °C, [α]D 25 -39.0 (c 1.0, CHCl3). IR (KBr): 1661, 1630, 1254, 1104 cm-1. 1H NMR (200 MHz, CDCl3): δ = 5.37 (s, 1 H, H-7), 4.26 (t, J = 4.8 Hz, 1 H, H-5), 4.12-4.05 (m, 2 H, Hdioxolane), 3.94-3.87 (m, 2 H, Hdioxolane), 2.76 and 2.60 (ABX, J = 13.7, 5.8, 4.4 Hz, 2 H, H-6), 1.92 (s,
3 H, H-8), 1.30 (s, 3 H, CH3) 1.22 (s, 3 H, CH3), 0.85 (s, 9 H, (CH3)3C-), 0.06 (s, 3 H, CH3-Si), 0.05 (s, 3 H, CH3-Si).
13C NMR (50 MHz, CDCl3): δ = 212.2 (C-1), 139.1 (C=), 133.0 (C=), 102.0 (CH-7), 72.2 (CH-5), 64.7 (CH2dioxolane), 64.4 (CH2dioxolane), 47.1 (C-2), 45.6 (CH2-6), 25.6 (CH3)3C-), 24.6 (CH3), 23.8 (CH3), 17.9 (CH3)3C-), 17.2 (CH3-8), -4.6 (CH3-Si), -4.8 (CH3-Si). Anal. Calcd for C18H32O4Si: C, 63.49; H, 9.47. Found: C, 63.67; H 9.45.