Mechanistic Divergence in the Hydrogenative Synthesis of Furans and Butenolides: Ruthenium Carbenes Formed by gem‐Hydrogenation or through Carbophilic Activation of Alkynes
Open Access
- 14 October 2019
- journal article
- research article
- Published by Wiley in Angewandte Chemie
- Vol. 58 (51), 18476-18481
- https://doi.org/10.1002/anie.201912161
Abstract
Enynes with a tethered carbonyl substituent are converted into substituted furan derivatives upon hydrogenation using [Cp*RuCl] 4 as the catalyst. Paradoxically, this transformation can occur along two distinct pathways, each of which proceeds via discrete pianostool ruthenium carbenes. In the first case, hydrogenation and carbene formation are synchronized (“gem‐hydrogenation”), whereas the second pathway comprises carbene formation via carbophilic activation of the triple bond, followed by hydrogenative catalyst recycling. Representative carbene intermediates of either route were characterized by X‐ray crystallography; the structural data prove that the attack of the carbonyl group onto the electrophilic carbene center follows a Bürgi‐Dunitz trajectory.Funding Information
- Max-Planck-Gesellschaft
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