o-Benzenedisulfonimide
as a Powerful and Recyclable Organocatalyst for the Nazarov Reaction

Margherita Barbero; Silvano Cadamuro; Annamaria Deagostino; Stefano Dughera; Paolo Larini; Ernesto G. Occhiato; Cristina Prandi; Silvia Tabasso; Rosaria Vulcano; Paolo Venturello

doi:10.1055/s-0029-1216819

PAPER

o-Benzenedisulfonimide as a Powerful and Recyclable Organocatalyst for the Nazarov Reaction

Margherita Barbero*^a, Silvano Cadamuro^a, Annamaria Deagostino^a, Stefano Dughera^a, Paolo Larini^a, Ernesto G. Occhiato^b, Cristina Prandi*^a, Silvia Tabasso^a, Rosaria Vulcano^a, Paolo Venturello^a
^a Dipartimento di Chimica Generale e Chimica Organica, Università, Via P. Giuria 7, 10125 Torino, Italy
Fax: +39(011)7642; e-Mail: cristina.prandi@unito.it; e-Mail: margherita.barbero@unito.it;
^b Dipartimento di Chimica Organica ‘U. Schiff’, and HeteroBioLab, Università di Firenze, Via della Lastruccia 13, 50019 Sesto Fiorentino, Italy

Abstract

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Abstract

o-Benzenedisulfonimide has been used for the first time as a Brønsted acid catalyst to induce electrocyclization of dienones into cyclopentenones (Nazarov reaction). The catalyst has been used in various organic solvents or under solvent-free conditions and it is entirely recoverable from the reaction mixture. The versatility and the effectiveness of the proposed procedure is demonstrated on a wide range of both activated and inactivated substrates.

Key words

Nazarov reaction - Brønsted acid - cyclization - organocatalysis - cyclopentenones

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Referenzen

References

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Unpublished results from these laboratories.

In experiments conducted on a 10-mmol scale, according to the conditions indicated in Table 1, entry 11, the catalyst has been recovered as already reported^¹¹d from the reaction mixture and recycled up to three times without a significant loss of catalytic activity.

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During the progress of the reaction, the TLC control revealed the conversion of the allyl derivatives 2b and 2d into an intermediate that precedes the formation of the final product.

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Compounds 2h-j have been unsuccessfully subjected to Nazarov cyclization under the following conditions: Amberlyst in CH₂Cl₂, Amberlyst in toluene at 60 ˚C, 5% Cu(OTf)₂ in CH₂Cl₂ at r.t.

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