Open Access
Development of an α′-hydroxy enone for the aminocatalytic asymmetric formal conjugate addition of aldehydes to acrylates, vinyl ketones and acrolein
(Royal Society of Chemistry, 2023) Odriozola Ibarguren, José Manuel; Razkin Lizarraga, Jesús; Lorea Revilla, Beñat; Mielgo, Antonia; García Castillo, Jesús María; Oiarbide, Mikel; Palomo, Claudio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Aminocatalytic asymmetric conjugate addition of aldehydes to Michael acceptors is a well established C-C bond forming methodology. However, various acrylic-type acceptors, including acrylic acid derivatives and acrolein, remain reluctant. Here we demonstrate that the internal H-bonding self-activation in α'-hydroxy enones allows them to react smoothly with enolizable aldehydes using commercially available aminocatalysts to afford adducts in good yields and high enantioselectivity. Straightforward conversion of the ketol moiety of these adducts into aldehyde, ketone and carboxylic acid functionalities offers an indirect, unified entry to products derived from acrolein, alkyl-vinyl ketones and acrylates, respectively.
Open Access
Asymmetric propionate aldol reactions of a chiral lithium enolate accessible from direct enolization with n-butyllithium
(ARKAT USA, Inc., 2005) Palomo, Claudio; Oiarbide, Mikel; Gómez Bengoa, Enrique; Mielgo, Antonia; González Rego, María Concepción; García Castillo, Jesús María; González Guerrero, Alberto; Odriozola Ibarguren, José Manuel; Bañuelos Villaverde, Patricia; Linden, Anthony; Química Aplicada; Kimika Aplikatua
The presented lithium enolate-based methodology is suitable for access to propionate syn-aldol motifs with high levels of stereocontrol. The reactive lithium enolate species is generated by direct treatment of a camphor-based chiral ethyl ketone with butyllithium, and is subsequently submitted to aldolization with a broad variety of aldehydes. The product aldols are obtained in uniformly high yields and high d.r. values (ranging from 91:9 to >98:2) irrespective of the aliphatic (both linear and branched chain), α,β-unsaturated, aromatic, or hetero-aromatic nature of the aldehyde employed. The crystallinity of most of the obtained adducts offers an easy access to almost 100% isomerically pure products upon a single recrystallisation. The auxiliary (1R)- (+)-camphor can be removed easily from the adducts for reuse, thereby producing the corresponding syn propionate aldols. This technology is implemented in the synthesis of a key subunit of the multi-drug resistance reversing agent hapalosin.
Open Access
Organocatalytic Michael addition of unactivated a-branched nitroalkanes to afford optically active tertiary nitrocompounds
(American Chemical Society, 2023) Lorea Revilla, Beñat; García-Urricelqui, Ane; Odriozola Ibarguren, José Manuel; Razkin Lizarraga, Jesús; Espinal Viguri, Maialen; Oiarbide, Mikel; Mielgo, Antonia; García Castillo, Jesús María; Palomo, Claudio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Gobierno de Navarra / Nafarroako Gobernua; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA18- 2022
The direct, asymmetric conjugate addition of unactivated ¿-branched nitroalkanes is developed based on the combined use of chiral amine/ureidoaminal bifunctional catalysts and a tunable acrylate template to provide tertiary nitrocompounds in 55¿80% isolated yields and high enantioselectivity (e.r. up to 96:4). Elaboration of the ketol moiety in thus obtained adducts allows a fast entry to not only carboxylic and aldehyde derivatives but also nitrile compounds and enantioenriched 5,5-disubstituted ¿-lactams.

Odriozola Ibarguren, José Manuel

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