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Reaccions intramolecualrs de radicals 2-indolilacil: aplicació a la síntesi de compostos indòlics
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[cat] La present Tesi Doctoral es situa en el context de les reaccions intramoleculars de radicals 2-indolilacil i està constituïda, d'acord amb els objectius inicials, per dues parts. La primera part centra l'atenció en les ciclacions de radicals 2-indolilacil en condicions reductores, emprant alquens com a acceptors radicalaris per a l'obtenció d'estructures que formen part de productes naturals i d'altres compostos bioactius. En aquest context s'ha aconseguit: - El desenvolupament d'un nou procediment d'anulació indòlica que permet accedir a cetones cícliques 1,2-fusionades amb l'indole. - La síntesi total de l'alcaloide (±)-guatambuïna i la síntesi formal de l'alcaloide olivacina. La segona part es situa en el context de les reaccions intramoleculars de radicals 2-indolilacil amb sistemes aromàtics. Els principals aconseguiments en aquesta part són: - La ciclació de radicals 2-indolilacil sobre anells de benzè en condicions no reductores (n-Bu6Sn2-hvper donar de manera eficient indolil fenil cetones tetracícliques. - La ciclació regioselectiva de radicals 2-indolilacil sobre piridines en condicions no reductores (n-Bu6Sn2-hv per donar indolil 4-piridil cetones tetracícliques. L'efectivitat d'aquest protocol radicalari permet el fàcil accés a elipticina quinones. - La ciclació de radicals 3-(3-quinolil)metil-2-indolilacil en condicions reductores (TTMSS-AIBN) per donar pentacicles relacionats amb la calotrixina, l'estat d'oxidació dels quals varia depenent del tipus de substituent del nitrogen indòlic. A partir d'un substrat convenientment substituït s'ha assolit la síntesi de l'alcaloide calotrixina B. - El desenvolupament d'un protocol "metal free" per a la ciclació de radicals 3-(3-quinolil)metil-2-indolilacil, en el qual es fa evident la importància del paper de l'AIBN en les reaccions de substitució homolítica aromàtica.
[eng] This thesis work is placed in the context of intramolecular reactions of 2- indolylacyl radicals. According with the initial objectives it's structured in two parts. The first part focus attention to the cyclisation of 2-indolylacyl radicals under reductive conditions, using alkenes as radical acceptors to obtain structures related with natural products and medicinal compounds. In this first part: - A new annulation procedure based on intramolecular reactions of 2- indolylacyl radicals have been developed. This procedure provides straightforward access to cyclic ketones fused to 1,2-position of the indole nucleus. - A total synthesis of the (±)-guatambuine and a formal synthesis of olivacine alkaloid have been achieved. The second part of the work is placed in the context of intramolecuar reactions of 2-indolylacyl radicals with aromatic systems. In this second part: - The cyclization of 2-indolylacyl radicals under non reductive conditions (n-Bu6Sn2-h"v"to give efficiently tetracyclic phenyl indolyl ketones have been studied. - Regioselective cyclization of 2-indolylacyl radicals upon pyridines under non reductive conditions (n-Bu6Sn2-h"v" to give tetracyclic indolyl 4-pyridyl ketones have been studied. The effectiveness of this radical protocol is illustrated by a fast synthetic entry to ellipticine quinones. - The cyclisation of 3-(3-quinolyl)methyl-2-indolylacyl radicals under TTMSS-AIBN conditions have been studied. This cyclisation provides an efficient synthetic entry to calothrixin-related pentacycles, which are obtained in a different oxidation state depending on the substitution at the indole nitrogen. The synthesis of calothrixin B has been achieved from a radical precursor suitably protected at the indole nitrogen. - A new metal-free protocol for the cyclisation of 3-(3-quinolyl)methyl-2- indolylacyl radicals that illustrates the determinant role of AIBN in homolytic aromatic substitutions have been developed.
[eng] This thesis work is placed in the context of intramolecular reactions of 2- indolylacyl radicals. According with the initial objectives it's structured in two parts. The first part focus attention to the cyclisation of 2-indolylacyl radicals under reductive conditions, using alkenes as radical acceptors to obtain structures related with natural products and medicinal compounds. In this first part: - A new annulation procedure based on intramolecular reactions of 2- indolylacyl radicals have been developed. This procedure provides straightforward access to cyclic ketones fused to 1,2-position of the indole nucleus. - A total synthesis of the (±)-guatambuine and a formal synthesis of olivacine alkaloid have been achieved. The second part of the work is placed in the context of intramolecuar reactions of 2-indolylacyl radicals with aromatic systems. In this second part: - The cyclization of 2-indolylacyl radicals under non reductive conditions (n-Bu6Sn2-h"v"to give efficiently tetracyclic phenyl indolyl ketones have been studied. - Regioselective cyclization of 2-indolylacyl radicals upon pyridines under non reductive conditions (n-Bu6Sn2-h"v" to give tetracyclic indolyl 4-pyridyl ketones have been studied. The effectiveness of this radical protocol is illustrated by a fast synthetic entry to ellipticine quinones. - The cyclisation of 3-(3-quinolyl)methyl-2-indolylacyl radicals under TTMSS-AIBN conditions have been studied. This cyclisation provides an efficient synthetic entry to calothrixin-related pentacycles, which are obtained in a different oxidation state depending on the substitution at the indole nitrogen. The synthesis of calothrixin B has been achieved from a radical precursor suitably protected at the indole nitrogen. - A new metal-free protocol for the cyclisation of 3-(3-quinolyl)methyl-2- indolylacyl radicals that illustrates the determinant role of AIBN in homolytic aromatic substitutions have been developed.
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FERRANDO RUANA, Francesc. Reaccions intramolecualrs de radicals 2-indolilacil: aplicació a la síntesi de compostos indòlics. ISBN 8469011561. [consulted: 18 of August of 2026]. Available at: https://hdl.handle.net/2445/34811