Cobalt(I)-Catalysed Reactions for the Synthesis of Acyclic 1,4-Dienes - Genesis of Two Synthetic Methods

Abstract

The search for atom-economic carbon-carbon bond-forming reactions initiated by low-valent cobalt complexes has led to two reactions that generate acyclic 1,4-dienes: the 1,4-hydrovinylation reaction of a terminal alkene with a 1,3-diene and the Alder-ene reaction of a terminal alkene with an internal alkyne.

The regioselective cobalt-catalysed Diels-Alder reaction of an alkyne and a 1,3-diene for the synthesis of cyclic 1,4-dienes led to its application in the synthesis of 1,3-dicarbonyl derivatives upon ozonolysis. Through applications of the cobalt-catalysed 1,4-hydrovinylation reaction, the synthesis of 1,3- or 1,4-dicarbonyl derivatives can be accomplished in a substrate-controlled process. For instance, 2,3-dimethylbuta-1,3-diene leads to acyclic 1,4-dienes via the cobalt-catalysed 1,4-hydrovinylation reaction which can then be converted into 1,3-carbonyls by ozonolysis. In contrast, the use of 2-(trimethylsiloxy)buta-1,3-diene generates γ,δ-unsaturated ketones, which can be converted into 1,4-dicarbonyl derivatives upon ozonolysis. Recently, studies into the synthesis of different types of polycarbonyl compounds in which the distance between the carbonyl groups can be altered have been initiated.

1 Introduction

2 The 1,4-Hydrovinylation Reaction

3 The Alder-ene Reaction

4 Stoking the Fire of the Hydrovinylation Reaction

5 The ‘Second Generation’ of 1,4-Hydrovinylation Processes

Key words

Alder-ene reactions - alkenes - alkynes - cobalt catalysis - dienes - hydrovinylations

References

• 1 Noyori R. Asymmetric Catalysis in Organic Synthesis   Wiley; New York: 1994. 
• Key references:
• 2a Brunner H. Reimer A. Bull. Soc. Chim. Fr.  1997,  134:  307 
• 2b Lautens M. Tam W. Lautens JC. Edwards LG. Crudden CM. Smith AC. J. Am. Chem. Soc.  1995,  117:  6863 
• 3a Hilt G. du Mesnil F.-X. Lüers S. Angew. Chem. Int. Ed.  2001,  40:  387 
• 3b Hilt G. du Mesnil F.-X. Tetrahedron Lett.  2000,  41:  6757 
• For selected references concerning 1,2-hydrovinylation reactions, see:
• 4a Jolly PW. Wilke G. In Applied Homogeneous Catalysis with Organometallic Compounds   Vol. 2:  Cornils B. Herrmann WA. Wiley-VCH; Weinheim / Germany: 2002.  p.1164 
• 4b RajanBabu TV. Chem. Rev.  2003,  103:  2845 
• 4c Smith CR. RajanBabu TV. Org. Lett.  2008,  10:  1657 
• 4d Lassauque N. Franciò G. Leitner W. Adv. Synth. Catal.  2009,  351:  3133 
• 4e Grutters MMP. Müller C. Vogt D. J. Am. Chem. Soc.  2006,  128:  7414 
• 4f Sharma RK. RajanBabu TV. J. Am. Chem. Soc.  2010,  132:  3295 
• 5 Hilt G. Danz M. Treutwein J. Org. Lett.  2009,  11:  3322 
• 6a Hilt G. Treutwein J. Angew. Chem. Int. Ed.  2007,  46:  8500 
• 6b Hilt G. Paul A. Treutwein J. Org. Lett.  2010,  12:  1536 
• Compare ref. 5 and
• 7a Hilt G. Erver F. Harms K. Org. Lett.  2011,  13:  304 
• with
• 7b Trost BM. Toste FD. Pinkerton AB. Chem. Rev.  2001,  101:  2067 
• 7c Trost BM. Toste FD. Tetrahedron Lett.  1999,  40:  7739 
• 7d Trost BM. Martos-Redruejo A. Org. Lett.  2009,  11:  1071 
• 8 Hilt G. Janikowski J. Angew. Chem. Int. Ed.  2008,  47:  5243 
• 9a Hilt G. Janikowski J. Hess W. Angew. Chem. Int. Ed.  2006,  45:  5204 
• 9b Hilt G. Janikowski J. Org. Lett.  2009,  11:  773 
• 10a Silva MA. Pellegrinet SC. Goodman JM. J. Org. Chem.  2003,  68:  4095 
• 10b Silva MA. Pellegrinet SC. Goodman JM. ARKIVOC  2003,  (X):  556 
• 10c Pellegrinet SC. Silva MA. Goodman JM. J. Am. Chem. Soc.  2001,  123:  8832 
• 10d Lee Y.-K. Singleton DA. J. Org. Chem.  1997,  62:  2255 
• 10e Singleton DA. Kim K. Martinez JP. Tetrahedron Lett.  1993,  34:  3071 
• 11 Mörschel P. Janikowski J. Hilt G. Frenking G. J. Am. Chem. Soc.  2008,  130:  8952 
• 12a Hilt G. Arndt M. Weske DF. Synthesis  2010,  1321 
• 12b Kersten L. Roesner S. Hilt G. Org. Lett.  2010,  12:  4920 
• 12c Arndt M. Reinhold A. Hilt G. J. Org. Chem.  2010,  75:  5203 
• 14 Aho JE. Salomäki E. Rissanen K. Pihko PM. Org. Lett.  2008,  10:  4179 

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Hilt, G.; Kuttner, J.; Erver, F. unpublished results.