Iron Corroles and Porphyrins as Very Efficient and Highly Selective Catalysts for the Reactions of α-Diazo Esters with Amines

Abstract

Iron corroles and porphyrins catalyze the reactions of amines with ethyl diazoacetate extremely efficiently, leading to complete and rapid conversion into N-substituted glycine ethyl esters by simultaneous addition of the substrates to the catalysts. The selectivity toward activation of the NH bonds is remarkable and quite different from other catalysts.

Key words

diazo compounds - iron - corroles - porphyrins - catalysis

References and Notes

• 1a Doyle MP. McKervey MA. Ye T. In Modern Catalytic Methods for Organic Synthesis with Diazo Compounds   John Wiley & Sons; New York: 1998. 
• 1b Singh GS. Curr. Org. Synth.  2005,  2:  377 
• 2a Burtoloso ACB. Correia CRD. J. Organomet. Chem.  2005,  690:  5636 
• 2b Huang H. Wang Y. Chen Z. Hu W. Adv. Synth. Catal.  2005,  347:  531 
• 2c Davis FA. Wu Y. Xu H. Zhang J. Org. Lett.  2004,  6:  4523 
• 2d Fructos MR. Belderrain TR. Nicasio MC. Nolan SP. Kaur H. Diaz-Requejo MM. Perez PJ. J. Am. Chem. Soc.  2004,  126:  10846 
• 3 Yates P. J. Am. Chem. Soc.  1952,  74:  5376 
• 4a Saegusa T. Ito Y. Kobayashi S. Hirota K. Shimizu T. Tetrahedron Lett.  1966,  6131 
• 4b Nicoud J.-F. Kagan HB. Tetrahedron Lett.  1971,  2065 
• 5 Paulissen R. Hayez E. Hubert AJ. Teyssie P. Tetrahedron Lett.  1974,  15:  607 
• 6a Morilla ME. Diaz-Requejo MM. Belderrain TR. Nicasio MC. Trofimenko S. Perez PJ. Chem. Commun.  2002,  2998 
• 6b Bachmann S. Fielenbach D. Jorgensen KA. Org. Biomol. Chem.  2004,  2:  3044 
• 7a Galardon E. Le Maux P. Simonneaux G. J. Chem. Soc., Perkin Trans. 1  1997,  2455 
• 7b Galardon E. Le Maux P. Simonneaux G. Tetrahedron  2000,  56:  615 
• 8a Simkhovich L. Mahammed A. Goldberg I. Gross Z. Chem. Eur. J.  2001,  7:  1041 
• 8b Simkhovich L. Goldberg I. Gross Z. J. Porphyrins Phthalocyanines  2002,  6:  439 
• 8c Saltsman I. Simkhovich L. Balazs YS. Goldberg I. Gross Z. Inorg. Chim. Acta  2004,  357:  3038 
• 9a Gross Z. Simkhovich L. Galili N. Chem. Commun.  1999,  599 
• 9b Simkhovich L. Gross Z. Tetrahedron Lett.  2001,  42:  8089 
• 10a Gross Z. Galili N. Saltsman I. Angew. Chem. Int. Ed.  1999,  38:  1427 
• 10b Simkhovich L. Galili N. Saltsman I. Goldberg I. Gross Z. Inorg. Chem.  2000,  39:  2704 
• 10c Simkhovich L. Goldberg I. Gross Z. Inorg. Chem.  2002,  41:  5433 
• 10d Simkhovich L. Gross Z. Inorg. Chem.  2004,  43:  6136 
• 11 Bryliakov KP. Talsi EP. Angew. Chem. Int. Ed.  2004,  43:  5228 
• 13 Gawinecki R. Kolehmainen E. Kucybala Z. Osmialowski B. Kauppinen R. Magn. Reson. Chem.  1998,  36:  848 
• 15a Wolf JR. Hamaker CG. Djukic JP. Kodadek T. Woo LK. J. Am. Chem. Soc.  1995,  117:  9194 
• 15b Gross Z. Galili N. Simkhovich L. Tetrahedron Lett.  1999,  40:  1571 

12

Quantitative reactions of amines with EDA: To a solution of catalyst (1 mg, 1-1.5 µmol) in argon-purged Et₂O (1.5 mL), a solution of EDA and substrate (1-1.5 mmol each) in Et₂O (0.5 mL) was added at once. The 4-Cl-, 4-CN-, and 3-CN-substituted products precipitated from the reaction mixture, while the products of other amines were obtained by evaporating the solvent and treatment of the solid material with cold Et₂O. Reported yields are of isolated products (0.2-0.3 g); their purity was checked by GC analysis (> 99% for all the products) and their identity was confirmed by NMR spectroscopy and comparison with published data.^2d,6a,13

14

All other amines that were examined so far (piperidine, N-methylaniline, propylamine) reacted similarly and these and many other results will soon be published.