4 years ago

Ir-Catalyzed Enantioselective, Intramolecular Silylation of Methyl C–H Bonds

Ir-Catalyzed Enantioselective, Intramolecular Silylation of Methyl C–H Bonds
Bo Su, John F. Hartwig
We report highly enantioselective intramolecular, silylations of unactivated, primary C(sp3)–H bonds. The reactions form dihydrobenzosiloles in high yields with excellent enantioselectivities by functionalization of enantiotopic methyl groups under mild conditions. The reaction is catalyzed by an iridium complex generated from [Ir(COD)OMe]2 and chiral dinitrogen ligands that we recently disclosed. The C–Si bonds in the enantioenriched dihydrobenzosiloles were further transformed to C–Cl, C–Br, C–I, and C–O bonds in final products. The potential of this reaction was illustrated by sequential C(sp3)–H and C(sp2)–H silylations and functionalizations, as well as diastereoselective C–H silylations of a chiral, natural-product derivative containing multiple types of C–H bonds. Preliminary mechanistic studies suggest that C–H cleavage is the rate-determining step.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b06679

DOI: 10.1021/jacs.7b06679

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.