Enynes with a tethered carbonyl substituent are converted into substituted furan derivatives upon hydrogenation using [Cp*RuCl] 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 by 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 on the electrophilic carbene center follows a Bürgi-Dunitz trajectory.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916381PMC
http://dx.doi.org/10.1002/anie.201912161DOI Listing

Publication Analysis

Top Keywords

ruthenium carbenes
8
carbophilic activation
8
carbene formation
8
mechanistic divergence
4
divergence hydrogenative
4
hydrogenative synthesis
4
synthesis furans
4
furans butenolides
4
butenolides ruthenium
4
carbenes formed
4

Similar Publications

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!