Metal-to-Ligand Ratio-Dependent Chemodivergent Asymmetric Synthesis

Min Zheng, Ke Gao, Haitao Qin, Guigen Li, Hongjian Lu

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Chemodivergent asymmetric synthesis was achieved by tuning the metal-to-ligand ratio in an organometallic catalytic system. Using N-(aroyloxy)phthalimide as the precursor of either an oxygen-centered aroyloxy radical or a nitrogen-centered phthalimidyl radical, enantioselective oxocyanation or aminocyanation of alkenes was achieved separately through a dual photoredox and copper catalysis. The metal-to-ligand ratio can exert chemoselective control while retaining the high enantiopurity of divergent products. Both reactions proceed efficiently with catalyst loading as low as 0.2 mol % and can be performed on a gram scale without loss of chemoselectivity or enantioselectivity. Chemodivergent asymmetric 1,5-aminocyanation or 1,5-oxocyanation of vinylcyclopropane can also be realized by this protocol. Mechanistic investigations involving electron paramagnetic resonance (EPR) experiments were performed to shed light on the stereochemical and chemodivergent results.

Original languageEnglish
Pages (from-to)22892-22899
Number of pages8
JournalAngewandte Chemie - International Edition
Volume60
Issue number42
DOIs
StatePublished - Oct 11 2021

Keywords

  • asymmetric catalysis
  • chemodivergence
  • cyanation
  • radicals

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