Synlett 2012(2): 239-242  
DOI: 10.1055/s-0031-1290121
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

α-Formylation of α-Substituted Ketones

Jamal Hassan, Christopher J. Richards*
School of Chemistry, University of East Anglia, Norwich, NR4 7TJ, UK
Fax: +44(1603)592003; e-Mail: Chris.Richards@uea.ac.uk;
Further Information

Publication History

Received 1 November 2011
Publication Date:
22 December 2011 (eFirst)

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Abstract

The reaction of (chloromethylene)dimethylammonium chloride (generated in situ from oxalyl chloride and DMF) with α-substituted ketones in CH2Cl2, followed by workup with aqueous NaHCO3, gave β-keto aldehydes containing an α-quaternary centre (8-88% yield).

Key words

aldehydes - enols - hydrolysis - ketones - tautomerism

    References

  • 1 Vilsmeier A. Haack A. Ber. Dtsch. Chem. Ges.  1927,  60:  119 
  • 2a Meth-Cohn O. Stanforth SP. In Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.777 
  • 2b Downie IM. Earle MJ. Heaney H. Shuhaibar KF. Tetrahedron  1993,  49:  4015 
  • 3 Reichardt C. Schagerer K. Angew. Chem., Int. Ed. Engl.  1973,  12:  323 
  • 4a Hepburn DR. Hudson HR. J. Chem. Soc., Perkin Trans. 1  1976,  754 
  • 4b Procopiou PA. Brodie AC. Deal MJ. Hayman DF. Tetrahedron Lett.  1993,  34:  7483 
  • 4c Procopiou PA. Brodie AC. Deal MJ. Hayman DF. Smith GM. J. Chem. Soc., Perkin Trans. 1  1996,  2249 
  • 4d Barrett AGM. Koike N. Procopiou PA. J. Chem. Soc., Chem. Commun.  1995,  1403 
  • 4e Barrett AGM. Braddock DC. James RA. Procopiou PA. Chem. Commun.  1997,  433 
  • 4f Barrett AGM. Braddock DC. James RA. Koike N. Procopiou PA. J. Org. Chem.  1998,  63:  6273 
  • 4g Kawano Y. Kaneko N. Mukaiyama T. Chem. Lett.  2005,  34:  1612 
  • 5a Jarrahpour A. Zarei M. Tetrahedron Lett.  2007,  48:  8712 
  • 5b Jarrahpour A. Zarei M. Tetrahedron  2009,  65:  2927 
  • 6 Marson CM. Tetrahedron  1992,  48:  3659 
  • 7 Reddy CP. Tanimoto S. Synthesis  1987,  575 
  • 8 van Boeckel CAA. Beetz T. Vos JN. de Jong AJM. Van Aelst SF. van den Bosch RH. Mertens JMR. van der Vlugt FA. J. Carbohydr. Chem.  1985,  4:  293 
  • 9 Martínez AG. Alvarez RM. Barcina JO. Cerero SM. Vilar ET. Fraile AG. Hanack M. Subramanian LR. J. Chem. Soc., Chem. Commun.  1990,  1571 
  • 10 Zhang S.-S. Wang Z.-Q. Xu M.-H. Lin G.-Q. Org. Lett.  2010,  12:  5546 
  • 11 Rodrigues CAB. de Matos MN. Guerreiro BMH. Gonçalves AML. Romão CC. Afonso CAM. Tetrahedron Lett.  2011,  52:  2803