Nickel-Catalyzed Electrophilic Amination of Organozinc Halides

Abstract

The nickel-catalyzed electrophilic amination of organozinc halides with O-benzoyl N,N-dialkyl hydroxylamines allows for the preparation of a variety of aryl and alkyl tertiary amines in good yield. The reaction is noteworthy for the mild reaction conditions employed (room temperature) and the ease of product purification (acid/base extractive work up).

Key words

amination - organometallic reagents - nickel - catalysis - umpolung

References

• 1 Knochel P. Millot N. Rodriguez AL. Tucker CE. Org. React.  2001,  58:  417 
• 2 Berman AM. Johnson JS. J. Am. Chem. Soc.  2004,  126:  5680 
• 3 Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 
• 4 Hartwig JF. In Handbook of Organopalladium Chemistry for Organic Synthesis   Vol. 1:  Negishi E.-i. Wiley; New York: 2002.  p.1051-1096  
• 5 Muci AR. Buchwald SL. Top. Curr. Chem.  2002,  219:  131 
• 6 Wolfe JP. Buchwald SL. J. Am. Chem. Soc.  1997,  119:  6054 
• 7 Tasler S. Lipshutz BH. J. Org. Chem.  2002,  68:  1190 
• 8 Desmarets C. Schneider R. Fort Y. J. Org. Chem.  2002,  67:  3029 
• 9 Erdik E. Ay M. Chem. Rev.  1989,  89:  1947 
• 10 Greck C. Genêt JP. Synlett  1997,  741 
• 11 Dembech P. Seconi G. Ricci A. Chem.-Eur. J.  2000,  6:  1281 
• 12 Erdik E. Daskapan T. J. Chem. Soc., Perkin Trans. 1  1999,  3139 
• 13 Narasaka K. Pure Appl. Chem.  2002,  74:  143 
• 14 Velarde-Ortiz R. Guijarro A. Rieke RD. Tetrahedron Lett.  1998,  39:  9157 
• 16 Sapountzis I. Knochel P. J. Am. Chem. Soc.  2002,  124:  9390 
• 17 Sapountzis I. Knochel P. Angew. Chem. Int. Ed.  2004,  43:  897 
• 18 Knochel P. Dohle W. Gommermann N. Kneisel FF. Kopp F. Korn T. Sapountzis I. Vu VA. Angew. Chem. Int. Ed.  2003,  42:  4302 
• 19 Berman AM. Johnson JS. J. Org. Chem.  2005,  70:  364 

15

Higher yields were obtained with this protocol relative to that using 1 equiv of ZnCl₂ (or ZnBr₂).