Issue 8, 2010
From the journal:

New Journal of Chemistry

Reduction of base-stabilized difluoroboranes to induce rearrangement reactions†‡

Makoto Yamashita,*a   Yoshitaka Aramakia  and  Kyoko Nozaki*a  

* Corresponding authors

a The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Japan
E-mail: makotoy@chembio.t.u-tokyo.ac.jp, nozaki@chembio.t.u-tokyo.ac.jp
Fax: +81 3 5841 7262
Tel: +81 3 5841 7263

Abstract

Lewis base-stabilized difluoroboranes 2, 4-pyr and 4-iPr, having an oxazoline- or amine-tethered amide ligand, were synthesized and fully characterized. The treatment of 2 with KC8 led to its complete consumption, and the rearranged product 5-H, probably originating from C–O bond cleavage and B–O bond formation, could be isolated as a major Dip-containing product in 18% yield. From deuterium labelling experiments and diffusion control reactions, the formation of 5-H could be explained by a radical mechanism. The reduction of 4-pyr and 4-iPr using one-electron reducing agents also gave the rearranged products 13-pyr and 13-iPr in 21 and 19% yields, respectively, via C–N bond cleavage and B–N bond formation. The mechanism for the formation of 13-pyr and 13-iPr is suggested to contain a benzylic radical intermediate.

Graphical abstract: Reduction of base-stabilized difluoroboranes to induce rearrangement reactions

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Article information

DOI
https://doi.org/10.1039/C0NJ00363H
Article type
Paper
Submitted
13 May 2010
Accepted
06 Jul 2010
First published
09 Jul 2010

New J. Chem., 2010,34, 1774-1782

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Reduction of base-stabilized difluoroboranes to induce rearrangement reactions

M. Yamashita, Y. Aramaki and K. Nozaki, New J. Chem., 2010, 34, 1774 DOI: 10.1039/C0NJ00363H

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