γ-Selective C(sp3)–H amination via controlled migratory hydroamination

Changseok Lee, Huiyeong Seo, Jinwon Jeon and Sungwoo Hong ()
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Changseok Lee: Korea Advanced Institute of Science and Technology (KAIST)
Huiyeong Seo: Korea Advanced Institute of Science and Technology (KAIST)
Jinwon Jeon: Korea Advanced Institute of Science and Technology (KAIST)
Sungwoo Hong: Korea Advanced Institute of Science and Technology (KAIST)

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract Remote functionalization of alkenes via chain walking has generally been limited to C(sp3)–H bonds α and β to polar-functional units, while γ-C(sp3)–H functionalization through controlled alkene transposition is a longstanding challenge. Herein, we describe NiH-catalyzed migratory formal hydroamination of alkenyl amides achieved via chelation-assisted control, whereby various amino groups are installed at the γ-position of aliphatic chains. By tuning olefin isomerization and migratory hydroamination through ligand and directing group optimization, γ-selective amination can be achieved via stabilization of a 6-membered nickellacycle by an 8-aminoquinoline directing group and subsequent interception by an aminating reagent. A range of amines can be installed at the γ-C(sp3)–H bond of unactivated alkenes with varying alkyl chain lengths, enabling late-stage access to value-added γ-aminated products. Moreover, by employing picolinamide-coupled alkene substrates, this approach is further extended to δ-selective amination. The chain-walking mechanism and pathway selectivity are investigated by experimental and computational methods.

Date: 2021
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DOI: 10.1038/s41467-021-25696-z

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