General and versatile entry to 4,5-fused polycyclic imidazolones systems. Use of the tandem transposition/pi-cyclization of N-acyliminium species.
Identifieur interne : 000C12 ( France/Analysis ); précédent : 000C11; suivant : 000C13General and versatile entry to 4,5-fused polycyclic imidazolones systems. Use of the tandem transposition/pi-cyclization of N-acyliminium species.
Auteurs : Anthony Pesquet [France] ; Adam Daïch ; Luc Van HijfteSource :
- The Journal of organic chemistry [ 0022-3263 ] ; 2006.
English descriptors
- KwdEn :
- MESH :
- chemical , chemical synthesis : Imidazoles, Polycyclic Hydrocarbons, Aromatic.
- chemical , chemistry : Imidazoles, Ketones, Polycyclic Hydrocarbons, Aromatic.
- Cyclization, Molecular Structure, Stereoisomerism.
Abstract
A simple and efficient methodology for the synthesis of 4,5-fused imidazolidin-2-ones from bicyclic and tricyclic ketones in a four-step sequence was described, by successive spirohydantoin Bucherer-Berg formation, mono- and dialkylation of the nitrogen atom of the hydantoin ring, regioselective reduction of one carbonyl function, and cationic cyclization associated with ring expansion. The key step of this sequential reaction was based on a tandem transposition/intramolecular amidoalkylation of cyclic spiro-N-acyliminium species. The process seems to be easy, general, regiospecific, resulted in the formation of polyheterocyclic systems containing an imidazolidin-2-one nucleus in good to excellent yields (67-99%), and is compatible with a large-scale production (up to 3 g of product 14, for example). Also, this method allows the preparation of the novel heterocycles 14 and 15 that have pharmaceutically interesting profiles, which are not accessible through short current synthetic methods. Finally, products 15 bear a secondary amide function crucial for further transformations, including the introduction of various pharmacophore groups either at the C or the N atoms of the imidazole ring.
DOI: 10.1021/jo060616s
PubMed: 16808520
Affiliations:
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pubmed:16808520Le document en format XML
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The key step of this sequential reaction was based on a tandem transposition/intramolecular amidoalkylation of cyclic spiro-N-acyliminium species. The process seems to be easy, general, regiospecific, resulted in the formation of polyheterocyclic systems containing an imidazolidin-2-one nucleus in good to excellent yields (67-99%), and is compatible with a large-scale production (up to 3 g of product 14, for example). Also, this method allows the preparation of the novel heterocycles 14 and 15 that have pharmaceutically interesting profiles, which are not accessible through short current synthetic methods. Finally, products 15 bear a secondary amide function crucial for further transformations, including the introduction of various pharmacophore groups either at the C or the N atoms of the imidazole ring.</div></front></TEI><affiliations><list><country><li>France</li></country><region><li>Haute-Normandie</li><li>Région Normandie</li></region><settlement><li>Le Havre</li></settlement><orgName><li>Université du Havre</li></orgName></list><tree><noCountry><name sortKey="Daich, Adam" sort="Daich, Adam" uniqKey="Daich A" first="Adam" last="Daïch">Adam Daïch</name><name sortKey="Van Hijfte, Luc" sort="Van Hijfte, Luc" uniqKey="Van Hijfte L" first="Luc" last="Van Hijfte">Luc Van Hijfte</name></noCountry><country name="France"><region name="Région Normandie"><name sortKey="Pesquet, Anthony" sort="Pesquet, Anthony" uniqKey="Pesquet A" first="Anthony" last="Pesquet">Anthony Pesquet</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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