Rhodium- or Copper-Catalysed CH-Insertion of Carbenoids into Dihydro­aromatic Compounds and Acyclic 1,4-Dienes

Abstract

A straightforward reaction sequence consisting of a cobalt-catalysed Diels-Alder reaction for the generation of dihydro­aromatic compounds and a rhodium- or alternatively a copper-catalysed CH-insertion reaction of carbenoids from diazo esters generates highly substituted benzene derivatives. When acyclic 1,4-dienes are synthesised by a cobalt-catalysed 1,4-hydrovinylation reaction, the rhodium-catalysed conversion with diazo esters leads to cyclopropanation rather than CH-insertion products.

catalysis - cobalt - copper - cyclopropanation - 1,4-diene

References

For reviews see:

<A NAME="RZ07306SS-1A">1a</A> Campeau LC. Fagnou K. Chem. Commun.  2006,  1253 

<A NAME="RZ07306SS-1B">1b</A> Metal-catalyzed Cross-coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998. 

<A NAME="RZ07306SS-1C">1c</A> Tsuji J. Palladium Reagents Catalysts   Wiley-VCH; Weimheim: 1995. 

<A NAME="RZ07306SS-1D">1d</A> Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 

<A NAME="RZ07306SS-1E">1e</A> Sonogashira K. In Comprehensive Organic Synthesis   Vol. 3:  Trost BM. Fleming I. Pattenden G. Pergamon Press; New York: 1991.  p.521 

<A NAME="RZ07306SS-1F">1f</A> Negishi E. Anastasia L. Chem. Rev.  2003,  103:  1979 

For reviews see:

<A NAME="RZ07306SS-2A">2a</A> Davies HML. Loe O. Synthesis  2004,  2595 

<A NAME="RZ07306SS-2B">2b</A> Merlic CA. Zechman AL. Synthesis  2003,  1137 

<A NAME="RZ07306SS-2C">2c</A> Davies HML. Beckwith REJ. Chem. Rev.  2003,  103:  2861 

<A NAME="RZ07306SS-2D">2d</A> Lydon KM. McKervey MA. In Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; New York: 1999.  Chap. 16.2. p.539 

<A NAME="RZ07306SS-2E">2e</A> Dorwald FZ. Metal Carbenes in Organic Synthesis   Wiley-VCH; Weinheim: 1999. 

<A NAME="RZ07306SS-2F">2f</A> Arndtsen BA. Bergman RG. Mobley TA. Peterson TH. Acc. Chem. Res.  1995,  28:  154 

For selected recent examples see:

<A NAME="RZ07306SS-2G">2g</A> Davies HML. Jin Q. J. Am. Chem. Soc.  2004,  126:  10862 

<A NAME="RZ07306SS-2H">2h</A> Davies HML. Dal X. Long MS. J. Am. Chem. Soc.  2006,  128:  2485 

<A NAME="RZ07306SS-2I">2i</A> Davies HML. Manning JR. J. Am. Chem. Soc.  2006,  128:  1060 

<A NAME="RZ07306SS-2J">2j</A> Davies HML. Jin QH. Org. Lett.  2005,  7:  2293 

<A NAME="RZ07306SS-3A">3a</A> Davies HML. Gregg TM. Tetrahedron Lett.  2002,  43:  4951 

<A NAME="RZ07306SS-3B">3b</A> Davies HML. Walji AM. Townsend RJ. Tetrahedron Lett.  2002,  43:  4981 

<A NAME="RZ07306SS-3C">3c</A> Davies HML. Dai X. Long MS. J. Am. Chem. Soc.  2006,  128:  2485 

<A NAME="RZ07306SS-3D">3d</A> Davies HML. Manning JR. J. Am. Chem. Soc.  2006,  128:  1060 

<A NAME="RZ07306SS-3E">3e</A> Müller P. Tohill S. Tetrahedron  2000,  56:  1725 

For leading references, see:

<A NAME="RZ07306SS-4A">4a</A> Hilt G. Lüers S. Smolko KI. Org. Lett.  2005,  7:  251 

<A NAME="RZ07306SS-4B">4b</A> Hilt G. Lüers S. Harms K. J. Org. Chem.  2004,  69:  624 

<A NAME="RZ07306SS-4C">4c</A> Hilt G. Smolko KI. Angew. Chem. Int. Ed.  2003,  42:  2795 ; Angew. Chem. 2003, 115, 2901

<A NAME="RZ07306SS-5">5</A>

Hilt, G.; Galbiati, F. Org. Lett. 2006, 8, 2195

<A NAME="RZ07306SS-6A">6a</A> Kirmse W. Angew. Chem. Int. Ed.  2003,  42:  1088 ; Angew. Chem. 2003, 115, 1120

<A NAME="RZ07306SS-6B">6b</A> Doyle MP. Forbes DC. Chem. Rev.  1998,  98:  911 

<A NAME="RZ07306SS-6C">6c</A> Pfaltz A. In Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; New York: 1999.  Chap. 16.1. p.513 

<A NAME="RZ07306SS-7">7</A> Nozaki H. Moriuti S. Takaya H. Noyori R. Tetrahedron Lett.  1966,  7:  5239 

<A NAME="RZ07306SS-8">8</A> Hilt G. Galbiati F. Synlett  2005,  828 

<A NAME="RZ07306SS-9">9</A> Hilt G. Smolko KI. Lotsch BV. Synlett  2002,  1081 

For reviews, see:

<A NAME="RZ07306SS-10A">10a</A> Valahovic MT. Keane JM. Harman WD. In Modern Arene Chemistry   Astruc D. Wiley; New York: 2002.  p.297 

<A NAME="RZ07306SS-10B">10b</A> Pape AR. Kaliappan KP. Kündig EP. Chem. Rev.  2000,  100:  2917 

<A NAME="RZ07306SS-11A">11a</A> Hilt G. du Mesnil F.-X. Lüers S. Angew. Chem. Int. Ed.  2001,  40:  387 ; Angew. Chem. 2001, 113, 408

<A NAME="RZ07306SS-11B">11b</A> Hilt G. Lüers S. Synthesis  2002,  609