Structural Features of Diacyldodecaheterocycles with Pseudo- C 2 -Symmetry: Promising Stereoinductors for Divergent Synthesis of Chiral Alcohols.

Autor: Flores-Bernal GG; Department of Organic Chemistry, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala s/n, 11340 Mexico City, Mexico., Vargas-Díaz ME; Department of Organic Chemistry, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala s/n, 11340 Mexico City, Mexico., Jiménez-Vázquez HA; Department of Organic Chemistry, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala s/n, 11340 Mexico City, Mexico., Hernández-Rodríguez M; Department of Organic Chemistry, Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, 04510 Mexico City, Mexico., Zepeda-Vallejo LG; Department of Organic Chemistry, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala s/n, 11340 Mexico City, Mexico.
Jazyk: angličtina
Zdroj: ACS omega [ACS Omega] 2023 May 03; Vol. 8 (23), pp. 20611-20620. Date of Electronic Publication: 2023 May 03 (Print Publication: 2023).
DOI: 10.1021/acsomega.3c01161
Abstrakt: Pseudo- C 2 -symmetric dodecaheterocyclic structures, which possess two acyl/aroyl groups disposed on either a cis- or trans-relative configuration, were prepared from the naturally occurring (-)-(1 R )-myrtenal. Addition of Grignard reagents (RMgX) to the diastereoisomeric mixture of these compounds unexpectedly showed that nucleophilic additions to the two prochiral carbonyl centers gave the same stereochemical result in both cis/trans diastereoisomers, making unnecessary the separation of this mixture. Noticeably, both carbonyl groups showed different reactivity because one of them is attached to an acetalic carbon and the other to a thioacetalic carbon. Furthermore, addition of RMgX to the carbonyl attached to the former carbon takes place through the re face, while addition to the second one proceeds through the si face, thus affording the corresponding carbinols in a highly diastereoselective process. This structural feature allowed the sequential hydrolysis of both carbinols, yielding separately ( R )- and ( S )-1,2-diols after reduction with NaBH 4 . The mechanism of the asymmetric Grignard addition was explained by density functional theory calculations. This approach contributes to the development of the divergent synthesis of structurally and/or configurationally different chiral molecules.
Competing Interests: The authors declare no competing financial interest.
(© 2023 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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