HI-Catalyzed Hydroamination and Hydroarylation of Alkenes

Abstract

Aromatic amines react with alkenes in the presence of catalytic amounts of aqueous HI to give mixtures of the corresponding hydroamination and hydroarylation products. While the hydroamination reaction is the preferred pathway for aliphatic alkenes, the hydroarylation reaction becomes more important when styrenes are used as substrates. In general, the electronic properties of the alkene and the amine strongly influence the efficiency and the selectivity of the reaction.

Key words

alkenes - aminations - amines - homogeneous catalysis - iodine

References

• For reviews, see:
• 1a Müller TE. Beller M. Chem. Rev.  1998,  98:  675 
• 1b Brunet JJ. Neibecker D. In Catalytic Heterofunctionalization   Togni A. Grützmacher H. Wiley-VCH; Weinheim: 2001.  p.91-141  
• 1c Seayad J. Tillack A. Hartung CG. Beller M. Adv. Synth. Catal.  2002,  344:  795 
• 1d Pohlki F. Doye S. Chem. Soc. Rev.  2003,  32:  104 
• 1e Bytschkov I. Doye S. Eur. J. Org. Chem.  2003,  935 
• 1f Roesky PW. Müller TE. Angew. Chem. Int. Ed.  2003,  42:  2708 ; Angew. Chem. 2003, 115, 2812
• 1g Doye S. Synlett  2004,  1653 
• 1h Odom A. Dalton Trans.  2005,  225 
• 1i Hultzsch KC. Adv. Synth. Catal.  2005,  347:  367 
• 1j Hultzsch KC. Org. Biomol. Chem.  2005,  3:  1819 
• 2a Schlummer B. Hartwig JF. Org. Lett.  2002,  4:  1471 
• 2b For CF₃SO₃H-catalyzed hydroarylation of styrenes, see: Cherian AE. Domski GJ. Rose JM. Lobkovsky EB. Coates GW. Org. Lett.  2005,  7:  5135 
• 3 Anderson LL. Arnold J. Bergman RG. J. Am. Chem. Soc.  2005,  127:  14542 
• 4a Beller M. Thiel OR. Trauthwein H. Synlett  1999,  243 
• 4b Kawatsura M. Hartwig JF. J. Am. Chem. Soc.  2000,  122:  9546 
• 4c Takaya J. Hartwig JF. J. Am. Chem. Soc.  2005,  127:  5756 
• 4d Sakai N. Ridder A. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  8134 
• 5a Ackerman L. Kaspar LT. Gschrei CJ. Org. Lett.  2004,  6:  2515 
• 5b Kaspar LT. Fingerhut B. Ackermann L. Angew. Chem. Int. Ed.  2005,  44:  5972 ; Angew. Chem. 2005, 117, 6126
• For hydroaminations catalyzed by solid acid catalysts, see:
• 6a Beller M. Seayad J. Tillack A. Jiao H. Angew. Chem. Int. Ed.  2004,  43:  3368 ; Angew. Chem. 2004, 116, 3448; and references cited therein
• 6b

  See also reference 1b, and references cited therein.

• 7a Hickinbottom WJ. J. Chem. Soc.  1932,  2646 
• 7b Hickinbottom WJ. J. Chem. Soc.  1934,  319 
• 8 Hart H. Kosak JR. J. Org. Chem.  1962,  27:  116 
• 9 Kanner B. Heterocycles  1982,  18:  411