Person: García Castillo, Jesús María
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García Castillo
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Jesús María
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Ciencias
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InaMat2. Instituto de Investigación en Materiales Avanzados y Matemáticas
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0000-0001-6632-097X
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573
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Publication 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 - INAMAT2Aminocatalytic 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.Publication Open Access 4-Hydroxy-4-methylpent-1-en-3-one(Wiley, 2019) Palomo, Claudio; Oiarbide, Mikel; García Castillo, Jesús María; Ciencias; Zientziak[22082-43-5] C6H10O2 (MW 114.14) InChI = 1S/C6H10O2/c1-4-5(7)6(2,3)8/h4,8H,1H2,2-3H3 InChIKey = CANVUQXZGKVFSR-UHFFFAOYSA-N (electrophilic alkene used as an equivalent of acrylic acid and derived esters in Diels–Alder and 1,3-dipolar cycloaddition reactions, as well as conjugate addition reactions of carbon-centered nucleophiles, and also used as a surrogate of acrolein and vinyl ketones)Publication Open Access α-Hydroxy ketones as masked ester donors in Brønsted base catalyzed conjugate additions to nitroalkenes(Wiley, 2018) Olaizola, Iurre; Campano, Teresa E.; Iriarte, Igor; Vera, Silvia; Mielgo, Antonia; García Castillo, Jesús María; Odriozola Ibarguren, José Manuel; Oiarbide, Mikel; Palomo, Claudio; Institute for Advanced Materials and Mathematics - INAMAT2; Química Aplicada; Kimika AplikatuaThe catalyst-controlled enantioselective direct addition reaction of enolizable esters and related carboxylic acid derivatives to p electrophiles remains a difficult synthetic transformation. In this study, the suitability of a-hydroxy ketones as ester equivalents capable of being activated by bifunctional Brønsted base catalysts in the context of conjugate addition reactions to nitroolefins is demonstrated. The scope of the reaction, which affords the corresponding Michael adducts with very high stereoselectivity (diastereomeric ratio (d.r.) +95:5, up to 99% enantiomeric excess (ee)), and its limitations are explored, as is the aftermath elaboration of adducts into densely functionalized enantioenriched products.Publication 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 AplikatuaThe 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.Publication Open Access Organocatalytic Michael addition of unactivated a-branched nitroalkanes to afford optically active tertiary nitrocompounds(ACS, 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 GobernuaThe 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.Publication Open Access Asymmetric assembly of all‐carbon tertiary/quaternary nonadjacent stereocenters through organocatalytic conjugate addition of α‐cyanoacetates to a methacrylate equivalent(Wiley, 2016) Iriarte, Igor; Vera, Silvia; Badiola, Eider; Mielgo, Antonia; Oiarbide, Mikel; García Castillo, Jesús María; Odriozola Ibarguren, José Manuel; Palomo, Claudio; Química Aplicada; Kimika AplikatuaAn efficient, highly diastereo- and enantioselective assembly of acyclic carbonyl fragments possessing nonadjacent all-carbon tertiary/quaternary stereoarrays is reported based on a Brønsted base catalyzed Michael addition/a-protonation sequence involving a-cyanoacetates and 2,4-dimethyl-4-hydroxypenten-3-one as novel methacrylate equivalent.Publication Open Access Enantioselective addition of alkynyl ketones to nitroolefins assisted by Brønsted base/H-bonding catalysis(Wiley, 2019) Campano, Teresa E.; Iriarte, Igor; Olaizola, Olatz; Etxabe, Julen; Mielgo, Antonia; Ganboa, Iñaki; Odriozola Ibarguren, José Manuel; García Castillo, Jesús María; Oiarbide, Mikel; Palomo, Claudio; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; CienciasVarious sets of enolizable alkynyl ketones (including methyl ynones with α-aryl, α-alkenyl, and α-alkoxy groups) were able to react smoothly with nitroolefins with the assistance of bifunctional Brønsted base/H-bond catalysts to provide adducts with two consecutive tertiary stereocenters in a highly diastereo- and enantioselective fashion. Further transformation of the obtained adducts into optically active acyclic and polycyclic molecules, including some with intricate carbon skeletons, was also demonstrated.