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Methodologies for the synthesis of bioactive terpenes

Grant number: 11/13993-2
Support Opportunities:Regular Research Grants
Start date: December 01, 2011
End date: May 31, 2014
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Organic Chemistry
Principal Investigator:Timothy John Brocksom
Grantee:Timothy John Brocksom
Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil

Abstract

The synthesis of bioactive sesqui- and diterpenoids is of continuing relevance. We present two distinct methodologies for the synthesis of polycyclic systems associated with such natural products. The Diels-Alder reaction of para-benzoquinones and their nitrogen derivatives, with simple dienes, leads to bi- and tricyclic products with structures which are ready for transformation into various groups of terpenoids, with predictable chemo-, regio- and stereoselectivity. On the other hand, the ring expansion of (R)-(-)-carvone into a chiral enantiopure cycloheptenone, followed by alkylations and ring closing metathesis, leads to the perhydroazulene system found in several sesqui- and diterpenoids. The experimental work is being linked to computer calculations, from simple conformational analysis of intermediates, to the determination of activation energies of the reactions. (AU)

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Scientific publications (27)
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
MOMO, PATRICIA BETONI; PAVANI, CHRISTIANE; BAPTISTA, MAURICIO S.; BROCKSOM, TIMOTHY JOHN; DE OLIVEIRA, KLEBER THIAGO. Chemical Transformations and Photophysical Properties of meso-Tetrathienyl-Substituted Porphyrin Derivatives. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, n. 21, p. 4536-4547, . (11/13993-2, 13/07276-1, 12/50680-5)
DE SOUZA, JULIANA M.; GALAVERNA, RENAN; DE SOUZA, ALINE A. N.; BROCKSOM, TIMOTHY J.; PASTRE, JULIO C.; DE SOUZA, RODRIGO O. M. A.; DE OLIVEIRA, KLEBER T.. Impact of continuous flow chemistry in the synthesis of natural products and active pharmaceutical ingredients. Anais da Academia Brasileira de Ciências, v. 90, n. 2, p. 1131-1174, . (11/13993-2, 13/07276-1, 14/25770-6, 14/26378-2)
MOMO, PATRICIA B.; SAMPAIO, OLIVIA M.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Selective Vilsmeier-Haack aryl-formylations of tetrathienylporphyrin and its Ni(II) complex. Journal of Porphyrins and Phthalocyanines, v. 19, n. 6, p. 745-752, . (11/13993-2, 13/07276-1, 13/06532-4)
DE OLIVEIRA, KLEBER T.; MOMO, PATRICIA B.; DE ASSIS, FRANCISCO F.; FERREIRA, MARCO A. B.; BROCKSOM, TIMOTHY J.. Chlorins: Natural Sources, Synthetic Developments and Main Applications. CURRENT ORGANIC SYNTHESIS, v. 11, n. 1, p. 42-58, . (11/13993-2, 13/02311-3, 13/06532-4, 12/04964-1)
DONATONI, MARIA C.; JUNIOR, GILMAR A. B.; DE OLIVEIRA, KLEBER T.; ANDO, ROMULO A.; BROCKSOM, TIMOTHY J.; DOS SANTOS, ALCINDO A.. Solvent-free Diels-Alder reactions catalyzed by FeCl3 on Aerosil((R)) silica. Tetrahedron, v. 70, n. 20, p. 3231-3238, . (08/55401-1, 12/17093-9, 13/06532-4, 11/13993-2, 11/11613-8, 11/03244-2)
CARMONA-VARGAS, CHRISTIAN C.; ALVES, LEANDRO DE C.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Combining batch and continuous flow setups in the end-to-end synthesis of naturally occurring curcuminoids. REACTION CHEMISTRY & ENGINEERING, v. 2, n. 3, p. 366-374, . (11/13993-2, 13/07276-1, 15/21110-4, 15/11801-0)
DE SOUZA, JULIANA M.; DE ASSIS, FRANCISCO F.; CARVALHO, CARLA M. B.; CAVALEIRO, JOSE A. S.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Synthesis of non-aggregating chlorins and isobacteriochlorins from meso-tetralcis(pentafluorophenyl)porphyrin: a study using 1,3-dipolar cycloadditions under mild conditions. Tetrahedron Letters, v. 55, n. 8, p. 1491-1495, . (11/13993-2, 12/14328-5, 12/24096-4)
DE SOUZA, JULIANA M.; GALAVERNA, RENAN; DE SOUZA, ALINE A. N.; BROCKSOM, TIMOTHY J.; PASTRE, JULIO C.; DE SOUZA, RODRIGO O. M. A.; DE OLIVEIRA, KLEBER T.. Impact of continuous flow chemistry in the synthesis of natural products and active pharmaceutical ingredients. Anais da Academia Brasileira de Ciências, v. 90, p. 44-pg., . (14/25770-6, 14/26378-2, 13/07276-1, 11/13993-2)
MOMO, PATRICIA B.; SAMPAIO, OLIVIA M.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Selective Vilsmeier-Haack aryl-formylations of tetrathienylporphyrin and its Ni(II) complex. JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, v. 19, n. 6, p. 8-pg., . (13/06532-4, 13/07276-1, 11/13993-2)
BARTOLOMEU, ALOISIO DE A.; BROCKSOM, TIMOTHY J.; DA SILVA FILHO, LUIZ C.; DE OLIVEIRA, KLEBER T.. Multicomponent reactions mediated by NbCl5 for the synthesis of phthalonitrile-quinoline dyads: Methodology, scope, mechanistic insights and applications in phthalocyanine synthesis. DYES AND PIGMENTS, v. 151, p. 391-402, . (14/24506-3, 11/13993-2, 13/07276-1, 15/21110-4)
GOBO, NICHOLAS R. S.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Soluble and Non-Aggregated Phthalocyanines: Synthesis, Mechanistic Aspects and Their Main Building Blocks. CURRENT ORGANIC SYNTHESIS, v. 14, n. 8, p. 1132-1155, . (11/13993-2, 12/24092-9, 13/07276-1, 15/21110-4)
TIMOTHY J. BROCKSOM; KLEBER T. DE OLIVEIRA; ANDRÉ L. DESIDERÁ. The Chemistry of the Sesquiterpene Alkaloids. Journal of the Brazilian Chemical Society, v. 28, n. 6, p. 933-942, . (11/13993-2, 15/21110-4)
DE SOUZA, JULIANA M.; BROCKSOM, TIMOTHY J.; MCQUADE, D. TYLER; DE OLIVEIRA, KLEBER T.. Continuous Endoperoxidation of Conjugated Dienes and Subsequent Rearrangements Leading to C-H Oxidized Synthons. Journal of Organic Chemistry, v. 83, n. 15, p. 7574-7585, . (11/13993-2, 13/07276-1, 18/00106-7, 15/21110-4)
BARONA-CASTANO, JUAN C.; CARMONA-VARGAS, CHRISTIAN C.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. Porphyrins as Catalysts in Scalable Organic Reactions. Molecules, v. 21, n. 3, . (11/13993-2, 13/07276-1, 15/21110-4)
DIN, ZIA UD; FILL, TAICIA P.; CAROLINA DONATONI, M.; DOS SANTOS, CAROLINA A. A.; BROCKSOM, TIMOTHY J.; RODRIGUES-FILHO, E.. Microbial diversification of Diels-Alder cycloadducts by whole cells of Penicillium brasilianum. MOLECULAR DIVERSITY, v. 20, n. 4, p. 877-885, . (10/11384-6, 11/13993-2)
DE ASSIS, FRANCISCO F.; FERREIRA, MARCO A. B.; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.. NIR bacteriochlorin chromophores accessed by Heck and Sonogashira cross-coupling reactions on a tetrabromobacteriochlorin derivative. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 14, n. 4, p. 1402-1412, . (11/13993-2, 13/02311-3, 13/06532-4, 12/24096-4)
BARBOSA, LAYLA R.; VIEIRA, YGOR W.; LACERDA, JR., VALDEMAR; DE OLIVEIRA, KLEBER T.; DOS SANTOS, REGINALDO B.; GRECO, SANDRO J.; NETO, ALVARO C.; DE CASTRO, EUSTAQUIO V. R.; BROCKSOM, TIMOTHY J.. Unequivocal structural assignments of three cycloheptenoid intermediates for guaiane sesquiterpenes: an experimental and theoretical approach. Magnetic Resonance in Chemistry, v. 52, n. 6, p. 318-328, . (11/13993-2, 13/06532-4)
BROCKSOM, TIMOTHY JOHN; DESIDERA, ANDRE LUIZ; ALVES, LEANDRO DE CARVALHO; DE OLIVEIRA, KLEBER THIAGO. The New Directions of Organic Synthesis. CURRENT ORGANIC SYNTHESIS, v. 12, n. 5, p. 496-522, . (11/13993-2, 13/06532-4, 14/12001-4)
DONATONI, MARIA C.; VIEIRA, YGOR W.; BROCKSOM, TIMOTHY J.; RABELO, ADRIANO C.; LEITE, EDSON R.; DE OLIVEIRA, KLEBER T.. One-pot sequential functionalizations of meso-tetrathienylporphyrins via Heck-Mizoroki cross-coupling reactions. Tetrahedron Letters, v. 57, n. 27-28, p. 3016-3020, . (11/13993-2, 13/07276-1, 15/21110-4, 13/06532-4)
MOMO, PATRICIA B.; BELLETE, BARBARA S.; BROCKSOM, TIMOTHY J.; DE SOUZA, RODRIGO O. M. A.; DE OLIVEIRA, KLEBER T.. Exploiting novel process windows for the synthesis of meso-substituted porphyrins under continuous flow conditions. RSC ADVANCES, v. 5, n. 102, p. 84350-84355, . (11/13993-2, 13/07276-1, 13/06532-4)
ULIANA, MARCIANA P.; SERVILHA, BRUNO M.; ALEXOPOULOS, OLGA; DE OLIVEIRA, KLEBER T.; TORMENA, CLAUDIO F.; FERREIRA, MARCO A. B.; BROCKSOM, TIMOTHY J.. The Diels-Alder reactions of para-benzoquinone nitrogen-derivatives: an experimental and theoretical study. Tetrahedron, v. 70, n. 39, p. 6963-6973, . (11/13993-2, 13/02311-3, 13/06532-4)
ALVES, LEANDRO DE C.; DESIDERA, ANDRE L.; DE OLIVEIRA, KLEBER T.; NEWTON, SEAN; LEY, STEVEN V.; BROCKSOM, TIMOTHY J.. A practical deca-gram scale ring expansion of (R)-(-)-carvone to (R)-(+)-3-methyl-6-isopropenyl-cyclohept-3-enone-1. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 13, n. 28, p. 7633-7642, . (11/13993-2, 13/06532-4, 14/12001-4)
ULIANA, MARCIANA P.; PIRES, LAYLA; PRATAVIEIRA, SEBASTIAO; BROCKSOM, TIMOTHY J.; DE OLIVEIRA, KLEBER T.; BAGNATO, VANDERLEI S.; KURACHI, CRISTINA. Photobiological characteristics of chlorophyll a derivatives as microbial PDT agents. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v. 13, n. 8, p. 1137-1145, . (08/57858-9, 13/06532-4, 98/14270-8, 09/17476-2, 11/13993-2, 11/19720-8)
BRITO CARVALHO, CARLA MARISA; FUJITA, MARTA AKEMI; BROCKSOM, TIMOTHY JOHN; DE OLIVEIRA, KLEBER THIAGO. Synthesis and photophysical evaluations of beta-fused uracil-porphyrin derivatives. Tetrahedron, v. 69, n. 47, p. 9986-9993, . (11/17177-5, 11/13993-2, 12/04964-1)
ULIANA, MARCIANA PIERINA; RODRIGUES, ANDREIA DA CRUZ; ONO, BRUNO ANDRADE; PRATAVIEIRA, SEBASTIAO; DE OLIVEIRA, KLEBER THIAGO; KURACHI, CRISTINA. Photodynamic Inactivation of Microorganisms Using Semisynthetic Chlorophyll a Derivatives as Photosensitizers. Molecules, v. 27, n. 18, p. 14-pg., . (11/19720-8, 20/06874-6, 19/27176-8, 11/13993-2, 08/57858-9, 09/54035-4, 13/07276-1)
MOMO, PATRICIA BETONI; PAVANI, CHRISTIANE; BAPTISTA, MAURICIO S.; BROCKSOM, TIMOTHY JOHN; DE OLIVEIRA, KLEBER THIAGO. Chemical Transformations and Photophysical Properties of meso-Tetrathienyl-Substituted Porphyrin Derivatives. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, v. 2014, n. 21, p. 12-pg., . (12/50680-5, 13/07276-1, 11/13993-2)
DELLING, FELIX N.; ZUKERMAN-SCHPECTOR, JULIO; BROCKSOM, TIMOTHY J.; BROCKSOM, URSULA; FINELLI, FERNANDA G.; TIEKINK, EDWARD R. T.. (+/-)-(4aR,5R,8S,8aR)-8-(tert-Butyl-dimethylsilyloxy)-2,5,8a-trimethyl-4a, 5,8,8a-tetrahydronaphthalene-1,4-dione. ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, v. 69, p. 9-pg., . (11/13993-2)