Selective C(sp<sup>3</sup>)−N Bond Cleavage of <i>N</i>,<i>N</i>‐Dialkyl Tertiary Amines with the Loss of a Large Alkyl Group via an S<sub>N</sub>1 Pathway

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  • Jiaoyu Wu
    Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry & Materials Science Northwest University Xi'an 710127 China
  • Linqiang Li
    Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry & Materials Science Northwest University Xi'an 710127 China
  • Mengtian Liu
    Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry & Materials Science Northwest University Xi'an 710127 China
  • Lu Bai
    Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry & Materials Science Northwest University Xi'an 710127 China
  • Xinjun Luan
    Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education College of Chemistry & Materials Science Northwest University Xi'an 710127 China

説明

<jats:title>Abstract</jats:title><jats:p>Polar disconnection of the C(sp<jats:sup>3</jats:sup>)−N bond of N,N‐dialkyl‐substituted tertiary amines via ammonium species conventionally favored the loss of the smaller alkyl group by an S<jats:sub>N</jats:sub>2 displacement, while selective C(sp<jats:sup>3</jats:sup>)−N bond cleavage by cutting off the larger alkyl group is still underdeveloped. Herein, we present a novel Pd<jats:sup>0</jats:sup>‐catalyzed [2+2+1] annulation, proceeding through an alkyne‐directed palladacycle formation and consecutive diamination with a tertiary hydroxylamine by cleaving its N−O bond and one C(sp<jats:sup>3</jats:sup>)−N bond, for the rapid assembly of tricyclic indoles in a single‐step transformation. Noteworthy, experimental results indicated that large tert‐butyl and benzyl groups were selectively cleaved via an S<jats:sub>N</jats:sub>1 pathway, in the presence of a smaller alkyl group (Me, Et, <jats:sup><jats:italic>i</jats:italic></jats:sup>Pr). Under the guidance of this new finding, tricyclic indoles bearing a removable alkyl group could be exclusively obtained by using a (α‐methyl)benzyl/benzyl or tert‐butyl/2‐(methoxycarbonyl)ethyl mixed amino source.</jats:p>

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