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Palladium-Catalyzed Directed Atroposelective C–H Allylation via β-H Elimination: 1,1-Disubstituted Alkenes as Allyl Surrogates

Bei‐Bei Zhan, Zhen‐Sheng Jia, Jun Luo, Liang Jin, Xufeng Lin, Bing‐Feng Shi

2020Organic Letters44 citationsDOI

Abstract

Transition-metal-catalyzed dehydrogenative C-H allylation with 1,1-disubstituted alkenes via β-H elimination remains challenging, because of the low reactivity and difficulty of controlling selectivity. Herein, the development of a Pd(II)-catalyzed directed atroposelective C-H allylation with methacrylates is described. Exclusive allylic selectivity was achieved. A vast array of axially chiral biaryl-2-amines are efficiently synthesized with excellent enantioselectivities (up to >99% enantiomeric excess).

Topics & Concepts

ChemistryAllylic rearrangementSelectivityCatalysisPalladiumReactivity (psychology)EnantiomerCombinatorial chemistryMedicinal chemistryOrganic chemistryPathologyAlternative medicineMedicineAxial and Atropisomeric Chirality SynthesisCatalytic C–H Functionalization MethodsAlkaloids: synthesis and pharmacology
Palladium-Catalyzed Directed Atroposelective C–H Allylation via β-H Elimination: 1,1-Disubstituted Alkenes as Allyl Surrogates | Litcius