Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species. Issue 48 (6th October 2015)

• Record Type: Journal Article
• Authors: Perea‐Buceta, Jesus E.; Fernández, Israel; Heikkinen, Sami; Axenov, Kirill; King, Alistair W. T.; Niemi, Teemu; Nieger, Martin; Leskelä, Markku; Repo, Timo
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 48(2015)
• Page Start: 14321
• Page End: 14325
• Publication Date: 2015-10-06
• Subjects: density functional calculations -- homogeneous hydrogenation -- reaction mechanisms -- rhodium(I) -- Wilkinson's catalyst; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201506216
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The addition of Barton's base has a dramatic effect on the classic rhodium(III)‐mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored. Abstract : When Barton met Wilkinson : The simple addition of catalytic amounts of a strong Barton base to the well‐known hydrogenation reaction promoted by Wilkinson's catalyst leads to a significant amplification of the reactivity. This reactivity is due to the formation of highly active rhodium(I) monohydride species.