Cooperative Catalysis with Coupled Chiral Induction in 1,3‐Dipolar Cycloadditions of Azomethine Ylides

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Title: Cooperative Catalysis with Coupled Chiral Induction in 1,3‐Dipolar Cycloadditions of Azomethine Ylides
Authors: Cayuelas Rubio, Alberto | Larrañaga Agirre, Olatz | Selva, Verónica | Nájera, Carmen | Akiyama, Takahiko | Sansano, Jose M. | Cózar Ruano, Abel de | Miranda, José I. | Cossío Mora, Fernando Pedro
Research Group/s: Síntesis Asimétrica (SINTAS)
Center, Department or Service: Universidad de Alicante. Departamento de Química Orgánica | Universidad de Alicante. Instituto Universitario de Síntesis Orgánica
Keywords: Asymmetric catalysis | Cooperative catalysis | Cycloadditions | Density functional calculations | Enantioselective synthesis
Knowledge Area: Química Orgánica
Issue Date: 7-Jun-2018
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA
Citation: Chemistry - A European Journal. 2018, 24(32): 8092-8097. doi:10.1002/chem.201801433
Abstract: 1,3‐Dipolar cycloadditions (1,3‐DC) between imino esters (as precursors of N‐metallated azomethine ylides) and π‐deficient alkenes are promoted by cooperative asymmetric Lewis acid/Brønsted base catalysis. The components of these catalytic pairs are silver salts derived from enantiopure commercially available BINOL‐based phosphoric acids and Cinchona alkaloids. Chiral phosphoric silver(I) salts promote HOMO raising of in situ formed 1,3‐dipoles, whereas protonated cinchona alkaloids generate a LUMO lowering for the dipolarophiles resulting in a global acceleration of the 1,3‐DC. The best results were obtained with BINOL‐derived silver phosphate and hydrocinchonine. Matching between both cooperative metallo‐ and organocatalyst results in an enhanced enantiomeric excess, superior to that reached by both separate components. NOESY experiments and DFT calculations are compatible with a non‐covalent interaction (hydrogen bond) between both catalysts, which results in close contacts and mutually coupled chiral environments.
Sponsor: We gratefully acknowledge financial support from the Spanish Ministerio de Economía y Competitividad (MINECO) (projects CTQ2013-43446-P and CTQ2014-51912-REDC) the Spanish Ministerio de Economía, Industria y Competitividad, Agencia Estatal de Investigación (AEI) and Fondo Europeo de Desarrollo Regional (FEDER, EU) (projects CTQ2016-76782-P, CTQ2016-80375-P and CTQ2016-81797-REDC), the Generalitat Valenciana (PROMETEOII/2014/017), the Gobierno Vasco/ Eusko Jaurlaritza (GV/EJ, Grant IT673-13) and the University of Alicante. This work was partially supported by a Grant-in-Aid for Scientific Research from JSPS (17H03060).
ISSN: 0947-6539 (Print) | 1521-3765 (Online)
DOI: 10.1002/chem.201801433
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Peer Review: si
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Appears in Collections:INV - SINTAS - Artículos de Revistas

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