Cargando…

Enantioselective palladium-catalyzed C(sp(2))–C(sp(2)) σ bond activation of cyclopropenones by merging desymmetrization and (3 + 2) spiroannulation with cyclic 1,3-diketones

Catalytic asymmetric variants for functional group transformations based on carbon–carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp(2))–C(sp(2)) σ bond activation and click desymmetrization to form synthetically...

Descripción completa

Detalles Bibliográficos
Autores principales: Zhou, Han-Qi, Gu, Xing-Wei, Zhou, Xiao-Hua, Li, Li, Ye, Fei, Yin, Guan-Wu, Xu, Zheng, Xu, Li-Wen
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8549799/
https://www.ncbi.nlm.nih.gov/pubmed/34760158
http://dx.doi.org/10.1039/d1sc04558j
Descripción
Sumario:Catalytic asymmetric variants for functional group transformations based on carbon–carbon bond activation still remain elusive. Herein we present an unprecedented palladium-catalyzed (3 + 2) spiro-annulation merging C(sp(2))–C(sp(2)) σ bond activation and click desymmetrization to form synthetically versatile and value-added oxaspiro products. The operationally straightforward and enantioselective palladium-catalyzed atom-economic annulation process exploits a TADDOL-derived bulky P-ligand bearing a large cavity to control enantioselective spiro-annulation that converts cyclopropenones and cyclic 1,3-diketones into chiral oxaspiro cyclopentenone–lactone scaffolds with good diastereo- and enantio-selectivity. The click-like reaction is a successful methodology with a facile construction of two vicinal carbon quaternary stereocenters and can be used to deliver additional stereocenters during late-state functionalization for the synthesis of highly functionalized or more complex molecules.