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Synthesis 2012(9): 1293-1303  
DOI: 10.1055/s-0031-1289752
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Straightforward Synthesis of Nonconjugated Cyclohex-3-enone and Conjugated 4-Methylenecyclohex-2-enone Derivatives

Julian R. Kuttner, Svenja Warratz, Gerhard Hilt*
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße, 35043 Marburg, Germany
Fax: +49(6421)2825677; e-Mail: Hilt@chemie.uni-marburg.de;
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Publikationsverlauf

Received 16 January 2012
Publikationsdatum:
27. März 2012 (online)

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Abstract

The synthesis of nonconjugated cyclohex-3-enones via the regiodivergent cobalt-catalysed Diels-Alder reactions of 2-(trimethylsilyloxy)buta-1,3-diene with alkynes and hydrolysis of the dihydroaromatic intermediates is described. The application of bidentate phosphine ligands versus pyridine-imine ligands led to the regioselective formation of one out of the two possible regioisomeric products when terminal or unsymmetrically substituted alkynes were applied. The cyclohex-3-enone products were isolated mostly in good yields without isomerisation of the carbon-carbon double bond into conjugation based on the mild reaction conditions. The use of acetoxymethyl-substituted alkynes led to the conjugated 4-methylenecyclohex-2-enones after deprotection of the silyl enol ether.

Key words

alkynes - catalysis - cobalt - Diels-Alder reaction - dienes - nonconjugation

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6

Ligands: dppe = 1,2-bis(diphenylphosphino)ethane; py-imine = 2,4,6-trimethyl-N-(pyridin-2-ylmethylene)aniline.

7

In previous reactions the use of iron powder increased the chemo- and regioselectivity. In this series of experiments, the iron powder additive was not necessary and was therefore not added.

9

The catalysts with phosphine-type ligands show reactivity for the Diels-Alder reaction as well as for 1,4-hydrovinyl-ation. In contrast, catalysts with pyridine-imine-type ligands are unreactive in 1,4-hydrovinylation reactions thus far.