Borylation Directed Borylation of Indoles Using Pyrazabole Electrophiles: A One-Pot Route to C7-Borylated-Indolines
Jürgen Pahl1, Emily Noone1, Marina Uzelac1
1School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
Abstract:
Pyrazabole (1) is a readily accessible diboron compound that can be transformed into ditopic electrophiles. In 1 (and derivatives), the B⋅⋅⋅B separation is ca. 3 Å, appropriate for one boron centre bonding to N and one to the C7 of indoles and indolines. This suitable B⋅⋅⋅B separation enables double E-H (E=N/C) functionalisation of indoles and indolines. Specifically, the activation of 1 with HNTf2 generates an electrophile that transforms N-H indoles and indolines into N/C7-diborylated indolines, with N-H borylation directing subsequent C7-H borylation. Indole reduction to indoline occurs before C-H borylation and our studies indicate this proceeds via hydroboration-C3-protodeboronation to produce an intermediate that then undergoes C7 borylation. The borylated products can be converted in situ into C7-BPin-N-H-indolines. Overall, this represents a transient directed C-H borylation to form useful C7-BPin-indolines.
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