This research was supported by the Royal Society (M.J.I.), the Leverhulme Trust (E.R.C.), the EPSRC (I.A.C. and J.R.L.), and Cambridge Display Technologies (S.A.S.). We also acknowledge use of the EPSRC UK National Service for Computational Chemistry Software (NSCCS) for this research.
Haloboration of Internal Alkynes with Boronium and Borenium Cations as a Route to Tetrasubstituted Alkenes†
Article first published online: 5 JUN 2013
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons the Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.
Angewandte Chemie International Edition
Volume 52, Issue 29, pages 7518–7522, July 15, 2013
How to Cite
Lawson, J. R., Clark, E. R., Cade, I. A., Solomon, S. A. and Ingleson, M. J. (2013), Haloboration of Internal Alkynes with Boronium and Borenium Cations as a Route to Tetrasubstituted Alkenes . Angew. Chem. Int. Ed., 52: 7518–7522. doi: 10.1002/anie.201302609
- Issue published online: 11 JUL 2013
- Article first published online: 5 JUN 2013
- Manuscript Received: 28 MAR 2013
- Funded Access
- Royal Society
- Leverhulme Trust
- Cambridge Display Technologies
- borenium ions;
- boronate esters;
- synthetic methods;
- tetrasubstituted alkenes
Hail boration! 2-Dimethylaminopyridine-ligated dihaloborocations [X2B(2-DMAP)]+ with a strained four-membered boracycle were used for the haloboration of terminal and dialkyl internal alkynes (see scheme). Esterification then provided vinyl boronate esters as useful precursors to tetrasubstituted alkenes. Following mechanistic studies, the scope of the haloboration was expanded simply by variation of the amine. Pin=2,3-dimethyl-2,3-butanedioxy.