Download PDF
Synthesis 2011(9): 1347-1360  
DOI: 10.1055/s-0030-1259993
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Radical Zinc-Atom Transfer Based Multicomponent Approaches to 3-Alkylidene-Substituted Tetrahydrofurans

Fabrice Chemla*, Florian Dulong, Franck Ferreira, Max P. Nüllen, Alejandro Pérez-Luna*
Institut Parisien de Chimie Moléculaire (UMR 7201), FR 2769, UPMC Univ Paris 06, CNRS, Bâtiment F 2ème et., Case 183, 4 place Jussieu, 75005 Paris, France
Fax: +33(1)44277567; e-Mail: fabrice.chemla@upmc.fr; e-Mail: alejandro.perez_luna@upmc.fr;
Further Information

Publication History

Received 22 December 2010
Publication Date:
07 April 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

A domino 1,4-addition/alkyne carbozincation sequence based on a radical zinc-atom transfer process is disclosed. Two efficient multicomponent approaches to 3-alkylidenetetrahydrofurans from β-(propargyloxy)enoates bearing pendant alkynes (including ynamides) have been established: one involving the direct addition of dialkylzincs, and the second involving the dimethylzinc-mediated addition of alkyl iodides. Both sequences utilize the stereoselective formation of intermediate alkylidenezincs well suited for in situ functionalization with electrophiles.

1 Introduction

2 1,4-Addition/Cyclization of Dialkylzincs on β-(Propargyl­oxy)enoates

2.1 β-(Propargyloxy)enoates with a Pendant Terminal Alkyne

2.2 β-(Propargyloxy)enoates with a Pendant Substituted Alkyne

2.3 β-(Propargyloxy)enoates with a Pendant Ynamide

3 1,4-Addition/Cyclization of Alkylzinc Halides on β-(Propargyloxy)enoates

4 Dialkylzinc-Mediated 1,4-Addition/Cyclization of Alkyl Iodides on β-(Propargyloxy)enoates

5 Conclusion; Current and Future Work

Key words

zinc - radicals - tandem reaction - alkynes - metalation

    References

  • Reviews:
  • 1a Bazin S. Feray L. Bertrand MP. Chimia  2006,  60:  260 
    Google Scholar
  • 1b Akindele T. Yamada K.-i. Tomioka K. Acc. Chem. Res.  2009,  42:  345 
    Google Scholar
  • 2 Historical account, see: Seyferth D. Organometallics  2001,  20:  2940 
    CrossrefGoogle Scholar
  • 3a Lewinski J. Marciniac W. Lipkowski J. Justyniak I. J. Am. Chem. Soc.  2003,  125:  12698 
    Google Scholar
  • 3b Lewinski J. Sliwinski W. Dranka M. Justyniak I. Lipkowski J. Angew. Chem. Int. Ed.  2006,  45:  4826 
    Google Scholar
  • 3c Lewinski J. Suwala K. Kubisiak M. Ochal Z. Justyniak I. Lipkowski J. Angew. Chem. Int. Ed.  2008,  47:  7888 
    Google Scholar
  • 3d Lewinski J. Bury W. Dutkiewicz M. Maurin M. Justyniak I. Lipkowski J. Angew. Chem. Int. Ed.  2008,  47:  573 
    Google Scholar
  • 3e Lewinski J. Koscielski M. Suwala K. Justyniak I. Angew. Chem. Int. Ed.  2009,  48:  7017 
    Google Scholar
  • 3f Lewinski J. Suwala K. Kaczorowski T. Galezowski M. Gryko DT. Justyniak I. Lipkowski J. Chem. Commun.  2009,  215 
    Google Scholar
  • 4 Jana S. Berger RJF. Fröhlich R. Pape T. Mitzel NW. Inorg. Chem.  2007,  46:  4293 
    CrossrefGoogle Scholar
  • 5 Mileo E. Benfatti F. Cozzi PG. Lucarini M. Chem. Commun.  2009,  469 
    Google Scholar
  • 6 Maury J. Feray L. Bazin S. Clément J.-L. Marque SRA. Siri D. Bertrand MP. Chem. Eur. J.  2011,  17:  1586 
    CrossrefGoogle Scholar
  • 7 Davies AG. Roberts BP. Acc. Chem. Res.  1972,  387 ; and references cited therein
    Google Scholar
  • 8 For the first use of Et2Zn as radical mediator in the presence of oxygen in the context of synthesis, see: Ryu I. Araki F. Minakata S. Komatsu M. Tetrahedron Lett.  1998,  39:  6335 
    CrossrefGoogle Scholar
  • 9 Cohen T. Gibney H. Ivanov R. Yeh EA.-H. Marek I. Curran DP. J. Am. Chem. Soc.  2007,  129:  15405 
    CrossrefGoogle Scholar
  • 10a Bertrand MP. Feray L. Nouguier R. Perfetti P.
    J. Org. Chem.  1999,  64:  9189 
    Google Scholar
  • 10b Bazin S. Feray L. Siri D. Naubron J.-V. Bertrand MP. Chem. Commun.  2002,  2506 
    Google Scholar
  • 10c Bazin S. Feray L. Vanthuyne N. Bertrand MP. Tetrahedron  2005,  61:  4261 
    Google Scholar
  • 10d Bazin S. Feray L. Vanthuyne N. Siri D. Bertrand MP. Tetrahedron  2007,  63:  77 
    Google Scholar
  • 10e Maury J. Feray L. Perfetti P. Bertrand MP. Org. Lett.  2010,  12:  3590 
    Google Scholar
  • 11 Van der Deen H. Kellog RM. Feringa BL. Org. Lett.  2000,  2:  1593 
    CrossrefGoogle Scholar
  • 12a Miyabe H. Asada R. Yoshida K. Takemoto Y. Synlett  2004,  540 
    Google Scholar
  • 12b Miyabe H. Asada R. Takemoto Y. Tetrahedron  2005,  61:  385 
    Google Scholar
  • 13 Yamada K.-i. Umeki M. Maekawa M. Yamamoto Y. Akindele Y. Nakano M. Tomioka K. Tetrahedron  2008,  64:  7258 
    CrossrefGoogle Scholar
  • 14a Cozzi PG. Angew. Chem. Int. Ed.  2006,  45:  2951 
    Google Scholar
  • 14b Cozzi PG. Adv. Synth. Catal.  2006,  348:  2075 
    Google Scholar
  • 14c Cozzi PG. Mignogna A. Vicennati P. Adv. Synth. Catal.  2008,  350:  975 
    Google Scholar
  • 14d Fernández-Ibañez MA. Maciá B. Minnaard AJ. Feringa BL. Angew. Chem. Int. Ed.  2008,  47:  1317 
    Google Scholar
  • 14e Cozzi PG. Benfatti F. Guiteras Capdevila M. Mignogna A. Chem. Commun.  2008,  3317 
    Google Scholar
  • Furthermore, it has been proposed that transition-metal-promoted zinc/iodine exchange involves a radical mechanism, Cu(I):
  • 15a Rozema MJ. AchyuthaRao S. Knochel P. J. Org. Chem.  1992,  57:  1956 
    Google Scholar
  • Pd(0):
  • 15b Stadtmüller H. Vaupel A. Tucker CE. Stüdemann T. Knochel P. Chem. Eur. J.  1996,  2:  1204 
    Google Scholar
  • 15c Stadtmüller H. Lentz R. Tucker C. Stüdemann T. Dörner W. Knochel P. J. Am. Chem. Soc.  1993,  115:  7027 
    Google Scholar
  • Ni(0):
  • 15d Vaupel A. Knochel P. Tetrahedron Lett.  1994,  35:  8349 
    Google Scholar
  • 15e Vaupel A. Knochel P. J. Org. Chem.  1996,  61:  5743 
    Google Scholar
  • Mn(II)/Cu(I):
  • 15f Riguet E. Klement I. Kishan Reddy Ch. Cahiez G. Knochel P. Tetrahedron Lett.  1996,  37:  5865 
    Google Scholar
  • 16a Denes F. Chemla F. Normant J.-F. Angew. Chem. Int. Ed.  2003,  42:  4043 
    Google Scholar
  • 16b Denes F. Pérez-Luna A. Cutri S. Chemla F. Chem. Eur. J.  2006,  12:  6506 
    Google Scholar
  • 16c Denes F. Pérez-Luna A. Chemla F. J. Org. Chem.  2007,  72:  398 
    Google Scholar
  • 16d Giboulot S. Pérez-Luna A. Botuha C. Ferreira F. Chemla F. Tetrahedron Lett.  2008,  49:  3963 
    Google Scholar
  • 17 Feray L. Bertrand MP. Eur. J. Org. Chem.  2008,  3164 
    Google Scholar
  • 18 For a related photoinduced reaction, see: Charette AB. Beauchemin A. Marcoux J.-F. J. Am. Chem. Soc.  1998,  120:  5114 
    CrossrefGoogle Scholar
  • For important studies on radical formation by SET from dialkylzinc coordination complexes, see:
  • 19a Wissing E. Rijnberg E. van der Schaaf PA. van Gorp K. Boersma J. van Koten G. Organometallics  1994,  13:  2609 
    Google Scholar
  • 19b Wissing E. van der Linden S. Rijnberg E. Boersma J. Smeets WJJ. Spek AL. van Koten G. Organometallics  1994,  13:  2602 ; and references cited therein
    Google Scholar
  • 20 Chen Z. Zhang Y.-X. An Y. Song X.-L. Wang Y.-H. Zhu L.-L. Guo L. Eur. J. Org. Chem.  2009,  5146 
    Google Scholar
  • 22 Vinylcyclopentyl zinc has been prepared by reductive cyclization: Crandall JK. Ayers TA. Organometallics  1992,  11:  473 
    CrossrefGoogle Scholar
  • 23 Ni(II)-catalyzed intermolecular carbozincation, see: Stüdemann T. Knochel P. Angew. Chem. Int. Ed.  1997,  36:  93 
    CrossrefGoogle Scholar
  • 24 Pérez-Luna A. Botuha C. Ferreira F. Chemla F. Chem. Eur. J.  2008,  14:  8784 
    CrossrefGoogle Scholar
  • Selected examples:
  • 25a Bertrand MT. Courtois G. Migniniac L. Tetrahedron Lett.  1974,  15:  3147 
    Google Scholar
  • 25b Nakamura M. Fujimoto T. Endo K. Nakamura E. Org. Lett.  2004,  6:  4837 
    Google Scholar
  • 25c Cantagrel F. Pinet S. Gimbert Y. Chavant PY. Eur. J. Org. Chem.  2005,  2694 
    Google Scholar
  • Deprotonation of 1a responsible for the formation of 10 could also be effected by Bu2Zn, even though deprotonation of terminal alkynes by dialkylzincs in the absence of ligands is not a fast process, see:
  • 27a Okhlobystin OY. Zakharkin LI. J. Organomet. Chem.  1965,  3:  257 
    Google Scholar
  • 27b De Koning AJ. Van Rijn PE. Boersma J. Van der Kerk GJM. J. Organomet. Chem.  1979,  174:  129 
    Google Scholar
  • 27c Pinet S. Pandya SU. Chavant PY. Ayling A. Vallée Y. Org. Lett.  2002,  4:  1463 
    Google Scholar
  • 28 Cote A. Charette AB. J. Am. Chem. Soc.  2008,  130:  2771 
    CrossrefGoogle Scholar
  • 29 Haaland A. Green JC. McGrady GS. Downs AJ. Gullo E. Lyall MJ. Timberlake J. Tutukin AV. Volden HV. Ostby K.-A. Dalton Trans.  2003,  4356 
    Google Scholar
  • 30 Bamford CH. Newitt DM. J. Chem. Soc., Abstr.  1946,  688 
    Google Scholar
  • 32 Guijarro A. In The Chemistry of Organozinc Compounds   Rappoport Z. Marek I. Wiley; Chichester: 2007.  p.193-236  
    Google Scholar
  • 33 Jourmet M. Malacria M. J. Org. Chem.  1992,  57:  3085 
    CrossrefGoogle Scholar
  • 34 Curran DP. Chen M.-H. Kim DJ. J. Am. Chem. Soc.  1989,  111:  6265 
    CrossrefGoogle Scholar
  • Even though α-silyl stabilization of vinyl radicals leads to a tendency towards linearization:
  • 35a Lalitha S. Chandrasekhar J. Proc.-Indian Acad. Sci., Chem. Sci.  1994,  106:  259 ; they are better represented as very rapidly Z/E interconverting bent radicals:
    Google Scholar
  • 35b Rubin H. Fischer H. Helv. Chim. Acta  1996,  79:  1670 
    Google Scholar
  • 35c Bucher G. Mahajan AA. Schmittel M. J. Org. Chem.  2009,  74:  5850 
    Google Scholar
  • 36a Chechik-Lankin H. Livshin S. Marek I. Synlett  2005,  2098 
    Google Scholar
  • 36b Prakash Das J. Chechik H. Marek I. Nature Chem.  2009,  1:  128 
    Google Scholar
  • 37a Gourdet B. Lam HW. J. Am. Chem. Soc.  2009,  131:  3802 
    Google Scholar
  • 37b Gourdet B. Rudkin ME. Watts CA. Lam HW. J. Org. Chem.  2009,  74:  7849 
    Google Scholar
  • 38a Yasui H. Yorimitsu H. Oshima K. Chem. Lett.  2007,  36:  32 
    Google Scholar
  • 38b Yasui H. Yorimitsu H. Oshima K. Bull. Chem. Soc. Jpn.  2008,  81:  373 
    Google Scholar
  • 39 Marion F. Courillon C. Malacria M. Org. Lett.  2003,  5:  5095 
    CrossrefGoogle Scholar
  • 40a Sato A. Yorimitsu H. Oshima K. Synlett  2009,  28 
    Google Scholar
  • 40b Sato A. Yorimitsu H. Oshima K. Bull. Korean Chem. Soc.  2010,  31:  570 
    Google Scholar
  • 41 Banerjee B. Litvinov DN. Kang J. Bettale JD. Castle SL. Org. Lett.  2010,  12:  2650 
    CrossrefGoogle Scholar
  • 43a The Chemistry of Organozinc Compounds   Rappoport Z. Marek I. Wiley; Chichester: 2007. 
    Google Scholar
  • 43b Knochel P. Millot N. Rodrigues AL. Org. React.  2001,  58:  417 
    Google Scholar
  • 44 Blake AJ. Shannon J. Stephens JC. Woodward S. Chem. Eur. J.  2007,  13:  2462 
    CrossrefGoogle Scholar
  • 45 Beckwith ALJ. Tetrahedron  1981,  37:  3073 
    CrossrefGoogle Scholar
  • 46a Bertrand MP. Feray L. Nouguier R. Perfetti P. Synlett  1999,  1148 
    Google Scholar
  • 46b Bertrand MP. Coantic S. Feray L. Nouguier R. Perfetti P. Tetrahedron  2000,  56:  3951 
    Google Scholar
  • 47a Miyabe H. Ushiro C. Ueda M. Yamakawa K. Naito T. J. Org. Chem.  2000,  65:  176 
    Google Scholar
  • 47b Miyabe H. Konishi C. Naito T. Org. Lett.  2000,  2:  1443 
    Google Scholar
  • 48a Yamada K.-i. Yamamoto Y. Maekawa M. Akindele T. Umeki H. Tomioka K. Org. Lett.  2006,  8:  87 
    Google Scholar
  • 48b Yamada K.-i. Nakano Y. Maekawa M. Akindele T. Tomioka K. Org. Lett.  2008,  10:  3805 
    Google Scholar
  • 49a Vleeschouwer FD. Van Speybroeck V. Waroquier M. Geerlings P. De Proft F. Org. Lett.  2007,  9:  2721 
    Google Scholar
  • 49b Fischer H. Radom L. Angew. Chem. Int. Ed.  2001,  40:  1340 
    Google Scholar
  • 50 Similar stereoselectivities have been reported for other related iodine-atom transfer radical cascades, see for example: Miyabe H. Asada R. Toyoda A. Takemoto Y. Angew. Chem. Int. Ed.  2006,  45:  5863 
    CrossrefPubMedGoogle Scholar
  • See,
  • 51a Chinkov N. Tene D. Marek I. In Metal-Catalyzed Cross Coupling Reactions   2nd ed.:  Diederich D. de Meijere A. Wiley-VCH; New York: 2004.  p.395 
    Google Scholar
  • 51b Denès F. Pérez-Luna A. Chemla F. Chem. Rev.  2010,  110:  2366 
    Google Scholar
21

Reductive zincation of a vinyl radical has also been suggested to account for the formation of allenoates following zinc-mediated radical addition to propiolates, see ref. 17.

26

See the supporting information in ref. 24.

31

When CH2Cl2 was used as solvent, the Z/E ratio of product 5ha might not fully represent the diastereoselectivity of the zinc-atom transfer since in addition to these two diastereomers, a third tetrahydrofuran side product having incorporated a butyl residue was detected (∼20% yield in the crude) but could not be fully identified. In any case the diastereoselectivity of the reaction between 1h and Bu2Zn in CH2Cl2 should at best be mediocre.

42

See the Supporting Information.