Martínez García, LucasPrado, GustavoGoñez, Karen V.Paleo Pillado, María RitaSardina López, Francisco Javier2024-02-052024-02-052021Martínez-García, L., Prado, G. Góñez, K. V., Paleo, M.R., Sardina, F. J.(2021). Stereoselective Synthesis of Hydrindane and Hydroazulene Derivatives by Transannular Cyclization of Nine and Ten Membered Carbocycles. "Journal of Organic Chemistry", vol. 86, n. 19, 13684–136920022-3263http://hdl.handle.net/10347/32285This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © 2021 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.1c01751.Treatment of cis-fused bicyclic diene dicarboxylates with Li/naphthalene triggers a tandem ring-opening and transannular cyclization process that stereoselectively yields hydroazulenes and hydrindanes derivatives. Cyclononadienyl diesters, which can be isolated after the ring-opening step by judicious choice of the reaction conditions, undergo a tandem conjugate addition/intramolecular Michael addition upon treatment with chiral lithium amides to give bicyclic β-amino esters in a process where 4 contiguous stereocenters are formed with high diastereocontrol. A concise route toward the highly enantioenriched AEF ring core of the aconitine-type alkaloids has been developed as an application of this methodology. The starting cis-fused bicyclic dicarboxylates are easily prepared in one step by reductive alkylation of diisopropyl phthalate (Na/THF, followed by the appropriate bis-electrophiles).engCC BY-NC-ND 4.0http://creativecommons.org/licenses/by-nc-nd/4.0/CyclizationLayersMixturesOrganic compoundsSolutions230604 Química de los compuestos bicíclicosjournal article10.1021/acs.joc.1c017511520-6904open access