Hayashi Mikayo, Brown Lauren E, Porco John A
Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA).
Department of Chemistry, Center for Molecular Discovery, Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA),
European J Org Chem. 2016 Oct;2016(28):4800-4804. doi: 10.1002/ejoc.201601003.
Enantioenriched, polycyclic compounds were obtained from a simple acylphloroglucinol scaffold. Highly enantioselective dearomatization was accomplished using a Trost ligand-palladium(0) complex. A computational DFT model was developed to rationalize observed enantioselectivities and revealed a key reactant-ligand hydrogen bonding interaction. Dearomatized products were used in visible light-mediated photocycloadditions and oxidative free radical cyclizations to obtain novel polycyclic chemotypes including tricyclo[4.3.1.0]decan-10-ones, bicyclo[3.2.1]octan-8-ones and highly-substituted cycloheptanones.
对映体富集的多环化合物是从简单的酰基间苯三酚支架中获得的。使用特罗斯特配体-钯(0)络合物实现了高度对映选择性的去芳构化反应。开发了一个计算密度泛函理论(DFT)模型来解释观察到的对映选择性，并揭示了一种关键的反应物-配体氢键相互作用。去芳构化产物用于可见光介导的光环加成反应和氧化自由基环化反应，以获得新型的多环化学类型，包括三环[4.3.1.0]癸-10-酮、双环[3.2.1]辛-8-酮和高度取代的环庚酮。
