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Synthesis 2009(13): 2260-2266  
DOI: 10.1055/s-0029-1216819
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Margherita Barbero*a, Silvano Cadamuroa, Annamaria Deagostinoa, Stefano Dugheraa, Paolo Larinia, Ernesto G. Occhiatob, Cristina Prandi*a, Silvia Tabassoa, Rosaria Vulcanoa, Paolo Venturelloa
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
Further Information

Publication History

Received 13 February 2009
Publication Date:
14 May 2009 (online)

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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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14

Unpublished results from these laboratories.

15

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 reported¹¹d from the reaction mixture and recycled up to three times without a significant loss of catalytic activity.

17

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.

18

For an exhaustive discussion of the pattern of substitution of dienone on reactivity in Nazarov cyclization see ref. 3c and references therein. For effects of electron donor β-substi­-tuents see ref. 3f. For DFT calculations on reactivity of heterocyclic derivatives in Nazarov cyclization see ref. 12a and 12b.

19

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.