Theoretical study of reaction pathways for the rhodium phosphine-catalysed borylation of C-H bonds with pinacolborane

Dalton Transactions : an International Journal of Inorganic Chemistry
Wai Han LamTodd B Marder

Abstract

The reaction mechanism of the rhodium-phosphine catalysed borylation of methyl-substituted arenes using pinacolborane (HBpin) has been investigated theoretically using DFT calculations at the B3PW91 level. Factors affecting selectivity for benzylic vs. aromatic C-H bond activation have been examined. It was found that [Rh(PR3)2(H)] is the active species which oxidatively adds the C-H bond leading to an eta3-benzyl complex which is the key to determining the unusual benzylic regioselectivity observed experimentally for this catalyst system. Subsequent reaction with HBpin leads to a [Rh(PR3)2(eta3-benzyl)(H)(Bpin)] complex from which B-C reductive elimination provides product and regenerates the catalyst. The electrophilic nature of the boryl ligand assists in the reductive elimination process. In contrast to Ir(L)2(boryl)3-based catalysts, for which Ir(III)-Ir(V) cycles have been proposed, the Rh(I)-Rh(III) cycle is operating with the system addressed herein.

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Citations

Jun 17, 2006·Chemical Communications : Chem Comm·Simon AldridgeWilliam Clegg
Jul 2, 2009·Chemical Communications : Chem Comm·Li DangTodd B Marder
Jul 20, 2016·Chemical Reviews·Emily C NeeveTodd B Marder
Dec 7, 2013·The Journal of Organic Chemistry·Xiting ZhangCunyuan Zhao
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Feb 1, 2013·Angewandte Chemie·Holger BraunschweigKatharina Uttinger
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Jul 30, 2008·Chemistry : a European Journal·Holger BraunschweigKatharina Uttinger
Jun 17, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·David BreyerAnna Penner
Mar 15, 2012·Chemistry : a European Journal·Andrew G CrawfordTodd B Marder
Jan 13, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·P K Sajith, Cherumuttathu H Suresh
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