On the Origin of Regio- and Stereoselectivity in the Rhodium-Catalyzed Vinylarenes Hydroboration Reaction
- 18 March 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 69 (8) , 2669-2680
- https://doi.org/10.1021/jo035392h
Abstract
We studied the hydroboration of vinylarenes using rhodium complexes bearing atropoisomeric ligands. For the first time, an NMR spectroscopy study of the styrene and catecholborane addition to the precursor of catalyst [Rh(COD)(L−L)]BF4, where L−L = (R)-BINAP and (R)-QUINAP, showed evidence of the structure of intermediates involved in the catalytic cycle. On the basis of this evidence, and using DFT calculations and QM/MM strategies, we investigated the origin of regio- and stereoselectivity. We determined the structure and stability of the key intermediates for several ligands and substrates and found excellent agreement between the relative stability of the intermediates and the experimentally observed trends. Using model systems, we analyzed the role of the steric and electronic features of the ligands and the substrates in detail.Keywords
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