Cobalt(I)-Catalyzed Diels-Alder, 1,4-Hydrovinylation and 1,4-Hydrosilyl­ation Reactions of Non-Activated Starting Materials on a Large Scale

Abstract

The transformation of non-activated starting materials with a readily accessible and easy to handle catalyst system under ambient reaction conditions is of great value for the chemo- and regioselective generation of interesting building blocks in organic synthesis. Therefore, we present the large-scale application for the cobalt-catalyzed 1,4-hydrovinylation of 1,3-dienes with terminal alkenes (Scheme [1] ), the cobalt-catalyzed Diels-Alder reactions of various non-activated alkynes with 1,3-dienes and the cobalt-catalyzed 1,4-hydrosilylation of isoprene.

Key words

alkenes - alkynes - cobalt - Diels-Alder reaction - hydrovinylation - hydrosilylation

References

• 1a Carruthers W. Cycloaddition Reactions in Organic Synthesis   Pergamon Press; Oxford: 1990. 
• 1b Kobayashi S. Jørgensen KA. Cycloaddition Reactions in Organic Synthesis   Wiley-VCH; Weinheim: 2002. 
• 1c Corey EJ. Angew. Chem. Int. Ed.  2002,  41:  1650 ; Angew. Chem. 2002, 114, 1724
• 1d Nicolaou KC. Snyder SA. Montagnon T. Vassilikogiannakis GE. Angew. Chem. Int. Ed.  2002,  41:  1668 ; Angew. Chem. 2002, 114, 1743
• 2a Lautens M. Tam W. Lautens JC. Edwards LG. Crudden CM. Smith AC. J. Am. Chem. Soc.  1995,  117:  6863 
• 2b Chen Y. Kiattansakul R. Ma B. Snyder JK. J. Org. Chem.  2001,  66:  6932 
• 3 Hilt G. du Mesnil F.-X. Lüers S. Angew. Chem. Int. Ed.  2001,  40:  387 ; Angew. Chem. 2001, 113, 408
• 4 For a more detailed investigation upon sterical and electronic effects on the regiochemistry see: Hilt G. Lüers S. Synthesis  2002,  609 
• 5 Hilt G. du Mesnil F.-X. Tetrahedron Lett.  2000,  41:  6757 
• 6 Hilt G. Korn TJ. Tetrahedron Lett.  2001,  42:  2783 
• 7 Hilt G. Smolko KI. Synthesis  2002,  686 
• 8 Hilt G. Lüers S. Isr. J. Chem.  2001,  41:  317 
• 9 Hilt G. Smolko KI. Lotsch BV. Synlett  2002,  1081 
• 10 Hilt G. Lüers S. Synthesis  2003,  1784 
• 12 Hilt G. Smolko KI. Angew. Chem. Int. Ed.  2003,  43:  2795 ; Angew. Chem. 2003, 115, 2901
• 13 For an review upon 1,4-cyclohexadienes see: Alonso F. Yus M. Rec. Res. Dev. Org. Chem.  1999,  3:  9 
• Selected references for the hydrosilylation with various metal catalysts:
• 14a Brockmann M. Dieck HT. Kleinwächter I. J. Organomet. Chem.  1986,  309:  345 
• 14b Vaisarová V. Schraml J. Hetflejš J. Coll. Czech. Chem. Commun.  1978,  43:  265 
• 14c Čapka M. Hetflejš J. Coll. Czech. Chem. Commun.  1976,  41:  1024 
• 14d Lappert MF. Takahashi S. J. Chem. Soc., Chem. Commun.  1972,  1272 
• 14e Cornish AJ. Lappert MF. Nile LA. J. Organomet. Chem.  1977,  136:  73 
• 14f Ojima I. Donovan RJ. Clos N. Organometallics  1991,  10:  2606 
• 14g tom Dieck H. Kleinwächter I. Haupt ETK. J. Organomet. Chem.  1987,  321:  237 
• 14h Ojima I. Kumagai M. J. Organomet. Chem.  1978,  157:  359 
• 14i Gustafsson M. Frejd T. J. Chem. Soc., Perkin Trans 1  2002,  102 
• 14j Michalska ZM. Ostaszewski B. Strzelec K. J. Organomet. Chem.  1995,  496:  19 
• 14k Polizzi C. Caporusso AM. Vitulli G. Salvadori P. J. Organomet. Chem.  1993,  451:  C4 

11

Very recently we identified a nitrogen containing functional group (phthalimide) which allows the cobalt-catalysed cycloaddition with 1,3-dienes with our catalyst system.