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Synlett 2011(2): 199-202  
DOI: 10.1055/s-0030-1259281
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Microwave-Assisted Domino Hydroformylation without Syngas

Elena Cinia, Etienne Airiaub, Nicolas Girardb, André Mannb, Jessica Salvadoria, Maurizio Taddei*a
a Dipartimento Farmaco Chimico Tecnologico, Università degli Studi di Siena, Via A. Moro 2, 53100 Siena, Italy
Fax: +39(0577)234333; e-Mail: taddei.m@unisi.it;
b Laboratoire d’Innovation Thérapeutique, UMR 7200 CNRS-Université de Strasbourg, Faculté de Pharmacie, 74 route du Rhin, 67401 Illkirch, France
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Publication History

Received 15 October 2010
Publication Date:
23 December 2010 (online)

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Abstract

Hydroformylation is a powerful reaction that has suffered for some negative prejudices related to the use of gaseous H2 and CO. Now it is possible to carry out hydroformylation and different cyclohydrocarbonylations, even on complex substrates, using aqueous formalin as H2 and CO surrogate in few minutes under microwave irradiation. The catalytic system developed by Morimoto (Rh/BINAP for decomposition of formaldehyde and Rh/Xantphos for hydroformylation) is compatible with microwave dielectric heating and with complex substrates containing ligand atoms allowing rapid domino hydroformylation cyclization reactions without using the external supply of gaseous H2 and CO (gas cylinder) and without any particular safety limitation or device.

Key words

microwaves - hydroformylation - homogeneous catalysis - domino reactions

    Reference and Notes

  • 1a Chaudhari RV. Curr. Opin. Drug Discovery Dev.  2008,  11:  820 
    Google Scholar
  • 1b Breit B. Topics Curr. Chem.  2007,  279:  139 
    Google Scholar
  • 1c Breit B. Seiche W. Synthesis  2001,  1 
    Google Scholar
  • 1d van Leeuwen PWNM. In Rhodium-Catalyzed Hydroformylation   Kluwer; Dordrecht: 2000.  p.1 
    Google Scholar
  • 2 Bizzarri SN. Fenelon S. Ishikawa-Yamaki M. Chemical Economics Handbook   SRI International; Menlo Park USA: 1999.  p.682A 
    Google Scholar
  • Reviews:
  • 3a Eilbracht P. Bärfacker L. Buss C. Hollmann C. Kitsos-Rzychon BE. Kranemann CL. Rische T. Roggenbuck R. Schmidt A. Chem. Rev.  1999,  99:  3329 
    Google Scholar
  • 3b Eilbracht P. Schmidt AM. Top. Organomet. Chem.  2006,  18:  65 
    Google Scholar
  • 3c Breit B. Acc. Chem. Res.  2003,  36:  264 
    Google Scholar
  • Some selected recent examples:
  • 4a Vasylyev M. Alper H. Synthesis  2010,  2893 
    Google Scholar
  • 4b Airiau E. Spangenberg T. Girard N. Breit B. Mann A. Org. Lett.  2010,  12:  528 
    Google Scholar
  • 4c Dübon P. Farwick A. Helmchen G. Synlett  2009,  1413 
    Google Scholar
  • 4d Kemme ST. Smejkal T. Breit B. Adv. Synth. Catal.  2008,  350:  989 
    Google Scholar
  • 4e Chiou W.-H. Mizutani N. Ojima I. J. Org. Chem.  2007,  72:  1871 
    Google Scholar
  • 4f Padwa A. Bur SC. Tetrahedron  2007,  63:  5341 
    Google Scholar
  • 4g Teoh E. Campi EM. Jackson WR. Robinson AJ. Chem. Commun.  2002,  978 
    Google Scholar
  • 4h Hoffmann RW. Brückner D. Gerusz VJ. Heterocycles  2000,  52:  121 
    Google Scholar
  • 4i Bergmann DJ. Campi EM. Jackson WR. Patti AF. Chem. Commun.  1999,  1279 
    Google Scholar
  • 5 Ojima I. Tsai C.-Y. Tzamarioudaki M. Bonafoux D. Org. React.  2000,  56:  1 
    Google Scholar
  • 6a Seich W. Schuschkowski A. Breit B. Adv. Synth Catal.  2005,  347:  1488 
    Google Scholar
  • 6b Kemme ST. Smejkal T. Breit B. Chem. Eur. J.  2010,  16:  3423 
    Google Scholar
  • 7a Petricci E. Mann A. Rota A. Schoenfelder A. Taddei M. Org. Lett.  2006,  8:  3725 
    Google Scholar
  • 7b Petricci E. Mann A. Salvadori J. Taddei M. Tetrahedron Lett.  2007,  48:  8501 
    Google Scholar
  • 7c Salvadori J. Airiau E. Girard N. Mann A. Taddei M. Tetrahedron  2010,  66:  3749 
    Google Scholar
  • 7d Airiau E. Chemin C. Girard N. Lonzi G. Mann A. Petricci E. Salvadori J. Taddei M. Synthesis  2010,  2901 
    Google Scholar
  • 8 Makado G. Morimoto T. Sugimoto Y. Tsutsumi K. Kagawa N. Kakiuchia K. Adv. Synth. Catal.  2010,  352:  299 
    CrossrefGoogle Scholar
  • Some examples of the use of formaldehydes in hydroformylation:
  • 9a Smejkal T. Han H. Breit B. Krische MJ. J. Am. Chem. Soc.  2009,  131:  10366 
    Google Scholar
  • 9b Rosales M. Gonzalez A. Gonzalez B. Moratinos C. Perez H. Urdaneta J. Sanchez-Delgado RA. J. Organomet. Chem.  2005,  690:  3095 
    Google Scholar
  • 9c Ahn HS. Han SH. Uhm SJ. Seok WK. Lee HN. Korneeva GA. J. Mol. Catal. A: Chem.  1999,  144:  295 
    Google Scholar
  • 9d Kondo T. Akazome M. Tsuji Y. Watanabe W. J. Org. Chem.  1990,  55:  1286 
    Google Scholar
  • Degradation of formaldehyde in carbonylation reactions:
  • 10a Morimoto T. Yamasaki K. Hirano A. Tsutsumi K. Kagawa N. Kakiuchi K. Harada Y. Fukumoto Y. Chatani N. Nishioka T. Org. Lett.  2009,  11:  1777 
    Google Scholar
  • 10b Morimoto T. Fujioka M. Fuji K. Tsutsumi K. Kakiuchi K. J. Organomet. Chem.  2007,  692:  625 
    Google Scholar
  • 10c Morimoto T. Kiyomi K. Angew. Chem. Int. Ed.  2004,  43:  5580 
    Google Scholar
  • 11 Airiau E. Girard N. Mann A. Salvadori J. Taddei M. Org. Lett.  2009,  11:  5314 
    CrossrefGoogle Scholar
  • 12 Domino hydroformylation of compounds 11-13 was described in: Airiau E. Spangenberg T. Girard N. Schoenfelder A. Salvadori J. Taddei M. Mann A. Chem. Eur. J.  2008,  14:  10938 
    CrossrefGoogle Scholar
13

(3 S ,8a R )-3-Phenylhexahydro-5 H -[1,3]oxazolo[3,2- a ]-pyridin-5-one (20) - General Procedure
A MW vessel was charged with [RhCl(cod)]2 (2.5 mg, 0.005 mmol), BIPHEP (5.2 mg, 0.01 mmol), and Nixantphos (5.5 mg, 0.01 mmol) under nitrogen (the reaction was carried out without degassing the solution, an experiment done on a degassed solution, gave comparable results). After adding toluene (3 mL), alkene 11 (103 mg, 0.5 mmol), and formalin (37%, 205 µL, 2.5 mmol), the mixture was heated for 30
min at 90 ˚C by microwave irradiation at 250 W (value previously settled on the microwave oven, model Discover from CEM). The solvent was removed in vacuo and the product purified by column cromatography (eluent hexane-EtOAc, 4:1) and isolated as a waxy material (85 mg, 79% yield, dr > 98:2). Characterization as in ref. 12. Compounds 24-26 were described in ref. 7d and compound 28 in ref. 5. New compounds isolated in this work:
1-Oxaspiro[4.5]decan-2-ol (26) ¹H NMR (400 MHz, CDCl3): δ = 5.41 (s-like, 1 H), 3.85 (br s, 1 H), 2.11-1.90 (m, 4 H), 1.58-1.40 (m, 10 H). ¹³C NMR (100 MHz, CDCl3): δ = 100.7, 89.9, 38.7, 35.5, 34.4, 32.2, 25.8, 23.7). ESI-LRMS: m/z = 179 [M + Na]+, 157 [M + H]+.
5-Hydroxy-5-(6-hydroxytetrahydro-2 H -pyran-2-yl)-pentanal (27) ¹H NMR (400 MHz, CDCl3): δ = 9.77 (s, 1 Ha), 9.74 (t, J = 1.6 Hz, 1 Hb), 5.48 (s, 1 Ha, 1 Hb), 4.07-4.02 (m, 2 Ha, 2 Hb), 2.54-2.50 (m, 2 Ha), 2.48-2.44 (m, 2 Hb), 1.88-1.45 (m, 10 Ha, 10 Hb). ¹³C NMR (100 MHz, CDCl3): δ = 201.9, 102.1, 101.4, 78.8, 78.1, 43.2, 34.3, 30.5, 29.8, 28.0, 27.3, 23.9, 19.2, 17.7. ESI-LRMS: m/z = 257 [M + MeOH + Na]+.