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Síntesi estereoselectiva catalitzada per pal·ladi de sistemes poliòlics / Síntesis estereoselectiva catalizada por paladio de sistemas poliólicos
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[spa] En esta Tesis se han desarrollado metodologías para preparar polioles y poliaminoalcoholes a partir de 2-alquin-1,4-dioles empleando catálisis de paladio. La transformación de estos 1,4-dioles en 1,2-dioles y 1,2-aminoalcoholes protegidos en forma de acetales, carbonatos, acetatos o carbamatos se ha realizado estereoselectivamente mediante diferentes procesos de transferencia de quiralidad. En primer lugar, se estudió la preparación enantio- y diastereoselectiva de los 2-alquin-1,4-dioles basándonos en la adición de acetiluros de zinc a aldehídos mediada por BINOLes o aminoalcoholes quirales. En estas condiciones se pudieron sintetizar estereoselectivamente 1,4-dioles que poseían cadenas lineales y aromáticas. A continuación, se exploraron las transformaciones de 1,4-dioles en 1,2-dioles y 1,2-aminoalcoholes vía transferencia de quiralidad. Se intentó primero la formación de 1,2-dioles protegidos en forma de acetales empleando catálisis de Pd(II) con un éxito limitado debido a problemas de regio- y diastereoselectividad. Mucho más prometedora fue la preparación estereoselectiva de 1,2-dioles protegidos como carbonatos cíclicos. A partir de monocarbonatos derivados de 1,4-dioles y usando catálisis de Pd(0), se desarrolló una metodología para preparar trans-dioxolanonas que dieron acceso a sin-1,2-dioles. De la misma manera, la protección de los 1,4-dioles en forma de monocarbamatos permitió el acceso a trans-oxazolidinonas que permitieron la preparación de sin-1,2-aminoalcoholes. Por último, también se estudiaron procesos de inducción asimétrica del tipo 1,3. Así, a partir de 1,4-dioles protegidos en forma de diacetatos, se pudieron obtener estereoselectivamente 1,2-diacetatos sin o anti utilizando una transposición sigmatrópica [3,3] mediada por Pd(II). Finalmente, se han empleado las diferentes metodologías desarrolladas en esta Tesis para sintetizar el D-arabitol pentaacetate y un producto natural: la espicigerolida.
[eng] This Thesis comprehends various methodologies that we have developed for the preparation of polyols and polyaminoalcohols employing palladium catalysis and 2-alkyn-1,4-diols as starting materials. The transformation of this 1,4-diols into 1,2-diols and 1,2-aminoalcohols protected as their ketal, carbonate, acetate or carbamate derivatives has been carried out stereoselectively, applying in all cases a chirality transfer strategy. Firstly, we envisaged the preparation of 2-alkyn-1,4-diols by the enantio- and diastereoselective BINOL- or chiral aminoalcohol-mediated addition of zinc acetylides to aldehydes. The synthesis under the described conditions was stereoselective according to our expectations for linear and aromatic substituted 1,4-diols. With these substrates in hand we intended their transformation into 1,2-diols and 1,2-aminoalcohols relying on the aforementioned chirality transfer. The desired 1,2-diols were readily obtained as their ketal equivalents under Pd(II) catalysis, although with low regio- and diastereoselectivity. Improving on the latter strategy, we tried their obtention as cyclic carbonates, and were rewarded with gratifying results. Some 1,4-diols incorporating a monocarbonate moiety smoothly afforded trans-dioxolanones under Pd(0) catalysis, which are a form of protected syn-1,2-diols. Likewise, access to syn-1,2-aminoalcohols protected as their corresponding trans-oxazolidinones was obtained starting from the monocarbamate derivatives of the precursor 1,4-diols. The last methodology that was developed in the present Thesis dealt with a 1,3-asymmetric induction type process. Thus, diacetate derivatives of precursor 1,4-diols underwent a Pd(II)-mediated [3,3]-sigmatropic rearrangement and furnished stereoselectively either anti or syn 1,2-diacetates. Finally, we used the methodologies developed in this Thesis to obtain the D-arabitol pentaacetate and a natural compound: the spicigerolide.
[eng] This Thesis comprehends various methodologies that we have developed for the preparation of polyols and polyaminoalcohols employing palladium catalysis and 2-alkyn-1,4-diols as starting materials. The transformation of this 1,4-diols into 1,2-diols and 1,2-aminoalcohols protected as their ketal, carbonate, acetate or carbamate derivatives has been carried out stereoselectively, applying in all cases a chirality transfer strategy. Firstly, we envisaged the preparation of 2-alkyn-1,4-diols by the enantio- and diastereoselective BINOL- or chiral aminoalcohol-mediated addition of zinc acetylides to aldehydes. The synthesis under the described conditions was stereoselective according to our expectations for linear and aromatic substituted 1,4-diols. With these substrates in hand we intended their transformation into 1,2-diols and 1,2-aminoalcohols relying on the aforementioned chirality transfer. The desired 1,2-diols were readily obtained as their ketal equivalents under Pd(II) catalysis, although with low regio- and diastereoselectivity. Improving on the latter strategy, we tried their obtention as cyclic carbonates, and were rewarded with gratifying results. Some 1,4-diols incorporating a monocarbonate moiety smoothly afforded trans-dioxolanones under Pd(0) catalysis, which are a form of protected syn-1,2-diols. Likewise, access to syn-1,2-aminoalcohols protected as their corresponding trans-oxazolidinones was obtained starting from the monocarbamate derivatives of the precursor 1,4-diols. The last methodology that was developed in the present Thesis dealt with a 1,3-asymmetric induction type process. Thus, diacetate derivatives of precursor 1,4-diols underwent a Pd(II)-mediated [3,3]-sigmatropic rearrangement and furnished stereoselectively either anti or syn 1,2-diacetates. Finally, we used the methodologies developed in this Thesis to obtain the D-arabitol pentaacetate and a natural compound: the spicigerolide.
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GEORGES, Yohan. Síntesi estereoselectiva catalitzada per pal·ladi de sistemes poliòlics / Síntesis estereoselectiva catalizada por paladio de sistemas poliólicos. ISBN 9788469076088. [consulted: 19 of August of 2026]. Available at: https://hdl.handle.net/2445/42925