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Synthesis 2010(17): 2915-2921  
DOI: 10.1055/s-0030-1257860
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Crucial Role of β-Elimination in Determining Regio- and Chemoselectivity of the Rhodium-Catalyzed Hydroformylation of N-Allylpyrroles: A New Approach to 5,6-Dihydroindolizines

Roberta Settambolo*
ICCOM-CNR, UOS di Pisa, Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy
e-Mail: settambolo@dcci.unipi.it;
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Publication History

Received 7 May 2010
Publication Date:
16 July 2010 (online)

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Abstract

Rhodium-catalyzed hydroformylation of the chiral (S)-3-alkyl-3-pyrrol-1-ylprop-1-enes at 100 atmospheres total pressure and 25 ˚C led to the preferential formation of the branched 3-alkyl-2-methyl-3-pyrrol-1-ylpropanals. At 30 atmospheres and 125 ˚C, the linear 4-alkyl-4-pyrrol-1-ylbutanals were obtained: these aldehydes are not the final products, but evolve into more stable 5,6-dihydroindolizines, with the same optical purity as the starting olefins, via a domino cyclization-dehydration process. According to the generally accepted mechanism for rhodium-catalyzed hydroformylation, the regioselectivity, and then the final chemoselectivity, can be rationalized by taking into account that while at room temperature no β-elimination occurs, at high temperature the β-elimination involves the branched rhodium-alkyl intermediate only.

Key words

β-elimination - hydroformylations - rhodium-alkyl complexes - N-allylated pyrroles - indolizines

    References

  • 1a Osborn JA. Wilkinson G. Young JF. Chem. Commun.  1965,  17 
    Google Scholar
  • 1b Evans D. Yagupsky G. Wilkinson G. J. Chem. Soc. A  1968,  2660 
    Google Scholar
  • 1c Evans D. Osborn JA. Wilkinson G. J. Chem. Soc. A  1968,  3133 
    Google Scholar
  • 1d Yagupsky G. Brown CK. Wilkinson G. J. Chem. Soc. A  1970,  1392 
    Google Scholar
  • 1e Brown CK. Wilkinson G.
    J. Chem. Soc. A  1970,  2753 
    Google Scholar
  • 2 Ghio C. Alagona G. Lazzaroni R. Eur. J. Inorg. Chem.  2009,  98 
    CrossrefGoogle Scholar
  • 3 Ojima I. Chem. Rev.  1988,  88:  1011 
    CrossrefGoogle Scholar
  • 4a Kalck P. Serein-Spiran F. New J. Chem.  1989,  13:  515 
    Google Scholar
  • 4b Lapidus AL. Rodin AP. Pruidze IG. Ugrak BI. Izv. Akad. Nauk SSSR, Ser. Khim.  1990,  7:  1661 
    Google Scholar
  • 5 Browning AF. Bacon AD. White C. Milner DJ.
    J. Mol. Catal.  1993,  83:  L11 
    Google Scholar
  • 6a Caiazzo A. Settambolo R. Uccello-Barretta G. Lazzaroni R. J. Organomet. Chem.  1997,  548:  279 
    Google Scholar
  • 6b Lazzaroni R. Settambolo R. Mariani M. Caiazzo A. J. Organomet. Chem.  1999,  592:  69 
    Google Scholar
  • 7a Settambolo R. Scamuzzi S. Caiazzo A. Lazzaroni R. Organometallics  1998,  17:  2127 
    Google Scholar
  • 7b Caiazzo A. Settambolo R. Pontorno L. Lazzaroni R. J. Organomet. Chem.  2000,  599:  298 
    Google Scholar
  • 8 Lazzaroni R. Settambolo R. Uccello-Barretta G. Organometallics  1995,  14:  4644 
    CrossrefGoogle Scholar
  • 9a Hanson BE. Davis NE. J. Chem. Educ.  1987,  64:  928 
    Google Scholar
  • 9b Lazzaroni R. Pertici P. Bertozzi S. Fabrizi G.
    J. Mol. Catal.  1990,  58:  75 
    Google Scholar
  • 10 Organic Syntheses via Metal Carbonyls   Wender I. Pino P. Wiley-Interscience; New York: 1977. 
    Google Scholar
  • 11 Lazzaroni R. Raffaelli A. Settambolo R. Bertozzi S. Vitulli G. J. Mol. Catal.  1989,  50:  1 
    Google Scholar
  • 12a Lazzaroni R. Settambolo R. Uccello-Barretta G. Caiazzo A. Scamuzzi S. J. Mol. Catal. A: Chem.  1999,  143:  123 
    Google Scholar
  • 12b Botteghi C. Cazzolato L. Marchetti M. Paganelli S. J. Org. Chem.  1995,  60:  6612 
    Google Scholar
  • 13a Lazzaroni R. Settambolo R. Rocchiccioli S. Paganelli S. Marchetti M. J. Organomet. Chem.  2005,  690:  1699 
    Google Scholar
  • 13b Lazzaroni R. Settambolo R. Raffaelli A. Pucci S. Vitulli G. J. Organomet. Chem.  1988,  339:  357 
    Google Scholar
  • 14 Lazzaroni R. Settambolo R. Prota G. Botteghi C. Paganelli S. Marchetti M. Inorg. Chim. Acta  2004,  357:  3079 
    CrossrefGoogle Scholar
  • 15 Uccello-Barretta G. Lazzaroni R. Settambolo R. Salvadori P. J. Organomet. Chem.  1991,  417:  111 
    CrossrefGoogle Scholar
  • 16 Koga N. Jin SQ. Morokuma K. J. Am. Chem. Soc.  1988,  110:  3417 
    CrossrefGoogle Scholar
  • 17 Matsubara T. Koga N. Ding Y. Musaev DG. Morokuma K. Organometallics  1997,  16:  1065 
    CrossrefGoogle Scholar
  • 18 Torrent M. Solà M. Frenking G. Chem. Rev.  2000,  100:  439 ; and references cited therein
    CrossrefGoogle Scholar
  • 19a Alagona G. Ghio C. Lazzaroni R. Settambolo R. Organometallics  2001,  20:  5394 
    Google Scholar
  • 19b Alagona G. Ghio C. Rocchiccioli S. J. Mol. Model.  2007,  13:  823 
    Google Scholar
  • 20 Decker SA. Cundari TR. Organometallics  2001,  20:  2827 
    CrossrefGoogle Scholar
  • 21 Decker SA. Cundari TR. New J. Chem.  2002,  26:  129 
    CrossrefGoogle Scholar
  • 22 Settambolo R. Rocchiccioli S. Uccello-Barretta G. Lazzaroni R. Lett. Org. Chem.  2007,  4:  388 
    CrossrefGoogle Scholar
  • 23 Settambolo R. Guazzelli G. Mandoli A. Lazzaroni R. Tetrahedron: Asymmetry  2004,  15:  1821 
    CrossrefGoogle Scholar
  • 24 Settambolo R. Guazzelli G. Mengali L. Mandoli A. Lazzaroni R. Tetrahedron: Asymmetry  2003,  14:  2491 ; and references cited therein
    CrossrefGoogle Scholar
  • 25 Lazzaroni R. Settambolo R. Caiazzo A. Hydroformylation with Unmodified Rhodium Catalysts, In Rhodium-Catalysed Hydroformylation   van Leeuwen PWNM. Claver C. Kluwer CMC; Dortrecht: 2000.  p.15 
    Google Scholar
  • 26a Abu-Gnim C. Amer I. J. Organomet. Chem.  1996,  516:  235 
    Google Scholar
  • 26b Amer I. Alper H. J. Am. Chem. Soc.  1990,  112:  3674 
    Google Scholar
  • 27a Bruekelman SP. Leach SE. Meakins GD. Tirel MD. J. Chem. Soc., Perkin Trans. 1  1984,  2801 
    Google Scholar
  • 27b Kashima C. Maruyama T. Fujioka Y. Harada K.
    J. Chem. Soc., Perkin Trans. 1  1989,  1041 
    Google Scholar
  • 28 Katritzky AR. Belyakov SA. Rachwal B. Moutou J.-L. J. Org. Chem.  1997,  62:  700 
    CrossrefGoogle Scholar
  • 29a Settambolo R. Heterocycles  2009,   79:   219 
    Google Scholar
  • 29b Guazzelli G. Lazzaroni R. Settambolo R. Beilstein J. Org. Chem.  2008,  4:  2 
    Google Scholar
  • 29c Daly JW. Prog. Chem. Org. Nat. Prod.  1982,  41:  205 
    Google Scholar