3 years ago

Taming a Vinyl Cation with a Simple Al(OTf)3 Catalyst To Promote C−C Bond Cleavage

Taming a Vinyl Cation with a Simple Al(OTf)3 Catalyst To Promote C−C Bond Cleavage
Helena Damsen, Liang Fu, Meike Niggemann
A detailed mechanistic investigation identified the stepwise nature of the 1,3-aryl shift, which enables our recently disclosed Al3+-catalyzed insertion of unactivated alkynes into the sp2–sp3 C−C bond of benzyl alcohols. The selectivity for the rearranged product was found to be induced by the continued coordination of the aluminum catalyst to the rearranging species, which is encouraged by a reversible background reaction. This participation of the catalyst beyond the ionization step is unique in the realm of carbocation driven reactions and opens up the possibility of a catalyst-induced chiral induction in the future. Furthermore, the study represents a rare example of detailed mechanistic analysis of a reaction with a product selectivity that changes with increasing conversion. Never let go aluminum! Continued participation of the catalyst in a carbocation-driven reaction proved responsible for the selective induction of a highly unusual 1,3-carbon shift. Detailed mechanistic analysis explains why a vinyl cation undergoes an unexpected rearrangement, resulting in the net insertion of unactivated alkynes into a C−C bond in benzylic alcohols.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700282

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.