In the last years, researchers in the field of Organic Chemistry have dedicated many efforts to the isolation, characterization and synthesis of insect pheromones, due to their potential utility in the plague control. The use of pheromones, either in combination with traps or by emission of fake signals to interfere the sexual pairing (and hence the proliferation), is an environmentally friendly alternative to the use of pesticides. Despite more than 100 chiral pheromones have been isolated and characterized at present, very few are known presenting a cyclobutane in their structure. The monoterpene (+)-grandisol has been identified as the main component of the sexual attractive pheromone segregated by the male of the cotton boll weevil Anthonomus grandis, a harmful plague that causes important economical losses. Its trans isomer, fraganol, has been identified in extracts of the plant Artemisia fragans. Another structurally related monoterpene is (+)-lineatin, essential component of de aggregation pheromone segregated by the females of the ambrosia beetle, Trypodendron lineatum, plague of the conifer forests of Europe and North-America. Since they were isolated, the cyclobutane structure and biological activity of these compounds have attracted the interest of many synthetic chemists.

During the last years we have been developing a research project directed to the asymmetric synthesis of cyclobutane pheromones. The key step is the [2+2] photocycloaddition reaction of properly substituted 2(5H)-furanones to unsaturated substrates. In this strategy the chirality source is the starting furanone. One of the aims of this project is the design of new synthetic sequences for preparing cyclobutane natural products and analogues.

 XIII European Symposiun on Organic Chemistry (ESOC 13)

Dubrovnik, Croacia; Setembre 2003

A new efficient synthesis of (+)-lineatin

Ramon Alibés, Pedro de March, Marta Figueredo, Josep Font i Marta Racamonde

Poster

poster PDF

VII Confererència Fèlix Serratosa 2003

Barcelona, Espanya; Gener 2003

De la patulina a la lineatina

Josep Font

Lecture (PL)

XIX IUPAC Symposium on Photochemistry

Budapest, Hungria; Juliol 2002

Photocycloaddition of 1,2-dichloroethylene to chiral 2(5H)-furanones: a highly diastereoselective approach to cyclobutane and cyclobutene derivatives

Ramon Alibés, Pedro de March, Marta Figueredo, Josep Font, Marta Racamonde i Albert Rustullet

Poster

poster PDF

Studies on the regio- and diastereoselectivity of the photocycloaddition of ketene diethyl acetal to chiral 2(5H)-furanones

Ramon Alibés, Pedro de March, Marta Figueredo, Josep Font, Marta Racamonde i Albert Rustullet

Poster

poster PDF

XIX Reunión Bienal de Química Orgánica

Carmona, Sevilla, Espanya; Juny 2002

Obtención de ciclobutenos quirales. Aproximación sintética a la (+)-lineatina

Ramon Alibés, Pedro de March, Marta Figueredo, Josep Font i Marta Racamonde

Oral Communication

abstract PDF

XI European Carbohydrate Symposiun

Lisboa, Portugal; Setembre 2001

Stereoselective synthesis of bioactive cyclobutane derivatives from carbohydrates

Josep Font

Lecture (PL)

abstract PDF

XII European Symposiun on Organic Chemistry (ESOC 12)

Groningen, Holanda; Juny 2001

C₂-Symmetric enantiopure a,b-butenolides as templates for asymmetric synthesis. Application to the synthesis of (+)-grandisol

Pedro de March, Marta Figueredo, Josep Font i Javier Raya

Oral Communication

abstract PDF

V Jornadas de Carbohidratos

Badajoz, Espanya; Juny 2000

Síntesis estereoselectiva de derivados ciclobutánicos a partir de carbohidratos

Josep Font

Lecture (IL)

abstract PDF

First Hispano-German Organic Chemistry Symposium

La Corunya, Espanya; Abril 2000

[2+2] Photocycloaddition on homochiral 2(5H)-furanones. Application to the synthesis of pheromones

Ramon Alibés

Lecture (IL)

abstract PDF

I Trobada de Joves Investigadors dels Països catalans

Sitges, Barcelona, Espanya; Gener 2000

Bis-a,b-butenolides enantiopures amb simetria C₂ com a substrats quirals en síntesi estereoselectiva. Aplicació a la síntesi del (+)-grandisol

Pere de March, Marta Figueredo, Josep Font i Javier Raya

Oral Communication

abstract PDF

XI European Symposiun on Organic Chemistry (ESOC 11)

Goteborg, Suecia; Juliol 1999

C₂-Symmetric enantiopure bis-a,b-butenolides as chiral template for diastereoselective synthesis. Photochemically induced transformations

Pedro de March, Marta Figueredo, Josep Font i  Javier Raya

Poster

 abstract PDF

    XVII IUPAC Symposium on Photochemistry

Sitges, Barcelona; Juliol 1998

[2+2]-Photocycloaddition reaction of C₂-symmetric enantiopure bis-a,b-butenolides with ethylene

Javier Raya, Pedro de March, Marta Figueredo i Josep Font

Poster

abstract PDF

X European Symposiun on Organic Chemistry (ESOC 10)

Basilea, Suiza; Juny 1997

Synthesis of bis-a,b-butenolides with C₂ symmetry

Javier Raya, Pedro de March, Marta Figueredo i Josep Font

Poster

abstract PDF

IX European Symposiun on Organic Chemistry (ESOC 9)

Varsovia, Polonia; 1995

Diastereoselective [2+2] photocycloaddition of 2(5H)-furanones to vinylene carbonate

José Luís Bourdelande, Josep Font i Anna Gregori

Poster

abstract PDF

XV IUPAC Symposium on Photochemistry

Praga, Republica Checa; Juliol 1994

Diastereoselective [2+2] photocycloaddition of alkenes to 2(5H)-furanones

Ramon Alibés, José Luís Bourdelande, Josep Font i Anna Gregori

Poster

abstract PDF

IV Encuentro Latinoamericano e Iberoamericano de Fotoquímica y Fotobiología

Valparaiso, Chile; Abril 1994

Fotocicloadición [2+2] de alquenos a 2(5H)-furanonas: diastereoselectividad

Ramon Alibés, José Luís Bourdelande, Josep Font i Anna Gregori

Poster

abstract PDF

VIII European Symposiun on Organic Chemistry (ESOC 8)

Sitges, Barcelona, Espanya; Setembre 1993

Efficient synthesis of (+)- and (-)-grandisol via diastereoselective [2+2] cycloaddition

Ramon Alibés, José Luís Bourdelande i Josep Font

Poster

abstract PDF

Alibés, R.; Bourdelande, J.L.; Gregori, A.; Font, J.; Rustullet, A.; Parella, T. "Stereoselective Synthesis of  [3.3.0]-fused g-butyrolactones of carbohydrates" J. Carbohydr. Chem. 2003, accepted.

de March, P.; Figueredo, M.; Font, J.; Raya, J.; Álvarez-Larena, A.; Piniella, J. F. "C₂-Symmetric enantiopure ethane-tethered bis(a,b-butenolides) as templates for asymmetric synthesis. Application to the synthesis of (+)-grandisol" J. Org. Chem. 2003, 68, 2437-2447.

Alibés, R.; de March, P.; Figueredo, M.; Font, J.; Xiaolin Fu; Racamonde, M.; Álvarez-Larena, A.; Piniella, J. F. "Photochemical [2+2] cycloaddition of acetylene to chiral 2(5H)-furanones" J. Org. Chem. 2003, 68, 1283-1289.

Alibés, R.; de March, P.; Figueredo, M.; Font, J.; Racamonde, M.; Rustullet, A.; Álvarez-Larena, A.; Piniella, J. F.; Parella, T. "Photocycloaddition of (Z)-1,2-dichloroethylene to enantiopure 2(5H)-furanones: an efficient strategy for the diastereoselective synthesis of cyclobutane and cyclobutene derivatives" Tetrahedron Lett. 2003, 44, 69-71.

Alibés, R.; de March, P.; Figueredo, M.; Font, J.; Racamonde, M. "Stereoselective [2+2] photocycloaddition of acetylene to chiral 2(5H)-furanones" Tetrahedron Lett. 2001, 42, 6695-6697.

Busqué, F.; de March, P.; Figueredo, M.; Font, J.; Margaretha, P.; Raya, J. "Regioselectivity of the intramolecular photocycloaddition of a,b-butenolides to a terminal alkene" Synthesis 2001, 1143-1148.

de March, P.; Figueredo, M.; Font, J.; Raya, J. "Highly efficient, enantioselective synthesis of (+)-grandisol from a C₂-symmetric bis(a,b-butenolide)" Org. Lett. 2000, 2, 163-165.

de March, P.; Figueredo, M.; Font, J.; Raya, J. "C₂-Symmetric enantiopure bis-a,b-butenolides as diastereoselective substrates in ethylene photocycloaddition" Tetrahedron Lett. 1999, 40, 2205-2208.

Gregori, A.; Alibés, R.; Bourdelande, J.L.; Font, J. "Highly diastereoselective [2+2] photocycloaddition of homochiral 2(5H)-Furanones to vinylene carbonate" Tetrahedron Lett. 1998, 39, 6961-6962.

Gregori, A.; Alibés, R.; Bourdelande, J.L.; Font, J. "Facile and stereoselective synthesis of fused g-butyrolactones of carbohydrates" Tetrahedron Lett. 1998, 39, 6963-6966.

Alibés, R.; Bourdelande, J.L. Font, J.; Parella, T. "Highly efficient and diastereoselective approaches to (+)- and (-)-grandisol". Tetrahedron 1996, 52, 1279-1292.

Alibés, R.; Bourdelande, J.L. Font, J.; Gregori, A. Parella,T. "[2+2] Photocycloaddition of homochiral 2(5H)-furanones to alkenes. First step for an efficient synthesis of (+)- and (-)-grandisol" Tetrahedron 1996, 52, 1267-1278 (1996).

Alibés, R.; Bourdelande, J.L. Font, J.;Gregori, A. "Diastereoselective [2+2] photocycloaddition of alkenes to 2(5H)-furanones". J. of the Brazilian Chem. Soc. 1995, 6, 119-121.  

Alibés, R.; Bourdelande, J.L. Font, J. "Diastereoselective and highly efficient radical approach to (1S,6R) and (1R,6S)-2,2,6-trimethyl-3-oxabicyclo[4.2.0]octadecane, key intermediates in the synthesis of (+)- and (-)-grandisol" Tetrahedron Lett. 1994, 35, 2587-2588.

Alibés, R.; Bourdelande, J.L. Font, J. "Highly efficient approach to (+)-grandisol via a diastereoselective [2+2] photocycloaddition to 2(5H)-furanones" Tetrahedron Lett. 1993, 34, 7455-7458.