Cobalt-Catalysed Transformations of 1,3,5-Hexatrienes on a Large Scale

Anastasia Schmidt; Elias Maiterth; Gerhard Hilt

doi:10.1055/s-0034-1378375

Synthesis, Inhaltsverzeichnis

Synthesis 2014; 46(15): 2040-2044
DOI: 10.1055/s-0034-1378375

practical synthetic procedures

Cobalt-Catalysed Transformations of 1,3,5-Hexatrienes on a Large Scale

Anastasia Schmidt

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany Fax: +49(6421)2825677 eMail: Hilt@chemie.uni-marburg.de

,

Elias Maiterth

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany Fax: +49(6421)2825677 eMail: Hilt@chemie.uni-marburg.de

,

Gerhard Hilt*

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany Fax: +49(6421)2825677 eMail: Hilt@chemie.uni-marburg.de

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Abstract

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Abstract

The cobalt-catalysed 1,4-hydrovinylation of an aryl-substituted 1,3,5-hexatriene was investigated on a large scale for the synthesis of a double-skipped 1,4,7-triene product. The reaction proceeds via a regioselective C–H activation of the alkene and the exclusive formation of the 4Z-double bond. The cobalt-catalysed 1,4-hexatrienylation of a butadiene derivative led exclusively to the desired all-E tetraene product. Finally, the cobalt-catalysed Diels–Alder reaction with trimethylsilyl-substituted alkynes was investigated. The cycloadducts were generated with excellent chemo- and regioselectivity to give the corresponding stilbene derivative.

Key words

alkenes - alkynes - cobalt - 1,3-dienes - Diels–Alder reaction - 1,3,5-hexatrienes - 1,4-hydrovinylation

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Referenzen

References

For reviews, see:

1a Broere DL. J, Ruijter E. Synthesis 2012; 44: 2639
1b Shibata Y, Tanaka K. Synthesis 2012; 44: 323
1c Dominguez G, Perez-Castells J. Chem. Soc. Rev. 2011; 40: 3430
1d Hua R, Abrenica MV. A, Wang P. Curr. Org. Chem. 2011; 5: 712
1e Shaaban MR, El-Sayed R, Elwahy AH. M. Tetrahedron 2011; 67: 6095
1f Pla-Quintana A, Roglans A. Molecules 2010; 15: 9230
1g Inglesby PA, Evans PA. Chem. Soc. Rev. 2010; 39: 2791
1h Galan BR, Rovis T. Angew. Chem. Int. Ed. 2009; 48: 2830
1i Tanaka K. Chem. Asian J. 2009; 4: 508
1j Shibata T, Tsuchikama K. Org. Biomol. Chem. 2008; 6: 1317
1k Agenet N, Busine O, Slowinski F, Gandon V, Aubert C, Malacria M. Org. React. 2007; 68: 1
1l Gandon V, Aubert C, Malacria M. Chem. Commun. 2006; 2209
1m Chopade PR, Louie J. Adv. Synth. Catal. 2006; 348: 2307

2a Pellissier H, Clavier H. Chem. Rev. 2014; 114: 2775
2b Aitken DJ, Eijsberg H, Frongia A, Ollivier J, Piras PP. Synthesis 2014; 46: 1
2c Lee H.-W, Kwong F.-Y. Eur. J. Org. Chem. 2010; 789
2d Laschat S, Becheanu A, Bell T, Baro A. Synlett 2005; 2547
2e Blanco-Urgoiti J, Añorbe L, Pérez-Serrano L, Domínguez G, Pérez-Castells J. Chem. Soc. Rev. 2004; 33: 32

3a Nishibayashi Y. Synthesis 2012; 44: 489
3b Miyake Y, Uemura S, Nishibayashi Y. ChemCatChem 2009; 1: 342
3c Omae I. Appl. Organomet. Chem. 2007; 21: 318
3d Diaz DD, Betancort JM, Martin VS. Synlett 2007; 343

Leading references:

4a Fiebig L, Kuttner J, Hilt G, Schwarzer M, Frenking G, Schmalz H.-G, Schäfer M. J. Org. Chem. 2013; 78: 10485
4b Erver F, Kuttner JR, Hilt G. J. Org. Chem. 2012; 77: 8375
4c Arndt M, Hilt G, Khlebnikov AF, Kozhushkov SI, de Meijere A. Eur. J. Org. Chem. 2012; 3112
4d Hilt G, Janikowski J. Org. Lett. 2009; 11: 773

5a Erver F, Hilt G. J. Org. Chem. 2012; 77: 5216
5b Hilt G, Erver F, Harms K. Org. Lett. 2011; 13: 304
5c Hilt G, Paul A, Treutwein J. Org. Lett. 2010; 12: 1536
5d Hilt G, Treutwein J. Angew. Chem. Int. Ed. 2007; 46: 8500

6a Wang C.-C, Lin P.-S, Cheng C.-H. J. Am. Chem. Soc. 2002; 124: 9696
6b Chang H.-T, Jayanth TT, Wang C.-C, Cheng C.-H. J. Am. Chem. Soc. 2007; 129: 12032

7a Timsina YN, Biswas S, RajanBabu TV. J. Am. Chem. Soc. 2014; 136: 6215
7b Schmidt A.; Hilt, G. Chem. Asian J. 2014, in press; DOI: 10.1002/asia.201402323.
7c Clark JR, Griffith JR, Diver ST. J. Am. Chem. Soc. 2013; 135: 3327
7d Pünner F, Schmidt A, Hilt G. Angew. Chem. Int. Ed. 2012; 51: 1270

8a Hilt G. Eur. J. Org. Chem. 2012; 4441
8b Kersten L, Hilt G. Adv. Synth. Catal. 2012; 354: 863

9a Arndt M, Dindaroğlu M, Schmalz H.-G, Hilt G. Synthesis 2012; 44: 3534
9b Arndt M, Dindaroğlu M, Schmalz H.-G, Hilt G. Org. Lett. 2011; 13: 6236
9c Erver F, Hilt G. Org. Lett. 2011; 13: 5700

10 Hilt G, Roesner S. Synthesis 2011; 662
11 Schmidt A, Hilt G. Org. Lett. 2013; 15: 2708
12 Hilt G, Danz M. Synthesis 2008; 2257