Diazo-Transfer Reactions to 1,3-Dicarbonyl Compounds with Tosyl Azide

Abstract

A practical protocol for the large-scale preparation of 2-diazo-1,3-dicarbonyl compounds is described by diazo-transfer reactions with tosyl azide followed by efficient chromatographic purifications on silica gel and/or alumina.

diazo compounds - ketones - esters - Regitz reaction - chromatography

References

For efforts to clarify the terminologies of MBFTs, see:

<A NAME="RZ52211SS-1A">1a</A> Tietze LF. Beifuss U. Angew. Chem., Int. Ed. Eng.  1993,  32:  131 

<A NAME="RZ52211SS-1B">1b</A> Tietze LF. Chem. Rev.  1996,  96:  115 

<A NAME="RZ52211SS-1C">1c</A> Domino Reactions in Organic Synthesis   Tietze LF. Brasche G. Gericke KM. Wiley-VCH; Weinheim: 2006. 

<A NAME="RZ52211SS-1D">1d</A> Multicomponent Reactions   Zhu J. Bienaymé H. Wiley-VCH; Weinheim: 2005. 

<A NAME="RZ52211SS-1E">1e</A> Coquerel Y. Boddaert T. Presset M. Mailhol D. Rodriguez J. In Ideas in Chemistry and Molecular Sciences: Advances in Synthetic Chemistry   Pignataro B. Wiley-VCH; Weinheim: 2010.  Chap. 9. p.187 

Reviews:

<A NAME="RZ52211SS-2A">2a</A> Bonne D. Coquerel Y. Constantieux T. Rodriguez J. Tetrahedron: Asymmetry  2010,  21:  1085 

<A NAME="RZ52211SS-2B">2b</A> Sanchez Duque MM. Allais C. Isambert N. Contantieux T. Rodriguez J. In Topics in Heterocyclic Chemistry   23:  Orru RV. Springer-Verlag; Berlin: 2010.  p.227 

<A NAME="RZ52211SS-3">3</A> Kirmse W. Eur. J. Org. Chem.  2002,  2193 

<A NAME="RZ52211SS-4A">4a</A> Presset M. Coquerel Y. Rodriguez J. J. Org. Chem.  2009,  74:  415 

<A NAME="RZ52211SS-4B">4b</A> Presset M. Coquerel Y. Rodriguez J. Org. Lett.  2009,  11:  5706 

<A NAME="RZ52211SS-4C">4c</A> Presset M. Coquerel Y. Rodriguez J. Org. Lett.  2010,  12:  4212 

<A NAME="RZ52211SS-4D">4d</A> Boddaert T. Coquerel Y. Rodriguez J. Chem. Eur. J.  2011,  17:  2048 

Reviews:

<A NAME="RZ52211SS-5A">5a</A> Zhang Z. Wang J. Tetrahedron  2008,  64:  6577 

<A NAME="RZ52211SS-5B">5b</A> Doyle MP. Ye T. McKervey MA. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds   Wiley; New York: 1998. 

<A NAME="RZ52211SS-6">6</A> Maas G. Angew. Chem. Int. Ed.  2009,  48:  8186 

<A NAME="RZ52211SS-7A">7a</A> Regitz M. Tetrahedron Lett.  1964,  1403 

<A NAME="RZ52211SS-7B">7b</A> Regitz M. Angew. Chem., Int. Ed. Engl.  1967,  6:  733 

<A NAME="RZ52211SS-7C">7c</A> Regitz M. Synthesis  1972,  351 

<A NAME="RZ52211SS-7D">7d</A> Regitz M. Hocker J. Liedhegener A. Org. Synth. Coll. Vol. 5   Wiley; New York: 1973.  p.183 

<A NAME="RZ52211SS-8">8</A> Explosive decompositions of TsN₃ have been reported at temperatures above 120 ˚C in: Hazen GG. Weinstock LM. Connell R. Bollinger FW. Synth. Commun.  1981,  11:  947 

<A NAME="RZ52211SS-9">9</A> Taber DF. Ruckle RE. Hennessy MJ. J. Org. Chem.  1986,  51:  4077 

<A NAME="RZ52211SS-10">10</A> Baum JS. Shook DA. Davies HML. Smith HD. Synth. Commun.  1987,  17:  1709 

<A NAME="RZ52211SS-11">11</A> Green GM. Peet NP. Metz WA. J. Org. Chem.  2001,  66:  2509 

<A NAME="RZ52211SS-12">12</A> Goddard-Borger ED. Stick RV. Org. Lett.  2007,  9:  3797 

<A NAME="RZ52211SS-13A">13a</A> Kitamura M. Tashiro N. Okauchi T. Synlett  2009,  2943 

<A NAME="RZ52211SS-13B">13b</A> Kitamura M. Tashiro N. Miyagawa S. Okauchi T. Synthesis  2011,  1037 

<A NAME="RZ52211SS-14">14</A> Chiang Y. Kresge AJ. Nikolaev VA. Popik VV.
J. Am. Chem. Soc.  1997,  119:  11183 

<A NAME="RZ52211SS-15">15</A> Oda M. Kasai M. Kitahara Y. Chem. Lett.  1977,  307 

<A NAME="RZ52211SS-16">16</A> Popik VV. Korneev SM. Nikolaev VA. Korobitsyna IK. Synthesis  1991,  195 

<A NAME="RZ52211SS-17">17</A> Davies JR. Kane PD. Moody CJ. Tetrahedron  2004,  60:  3967 

<A NAME="RZ52211SS-18">18</A> Kokel B. Viehe HG. Angew. Chem., Int. Ed. Engl.  1980,  19:  716