Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines

Jennifer L. Kennemur, Gregory D. Kortman, Kami L. Hull

Research output: Contribution to journalArticlepeer-review


The regiodivergent Rh-catalyzed hydrothiolation of allyl amines and imines is presented. Bidentate phosphine ligands with larger natural bite angles (βn ≥ 99°), for example, DPEphos, dpph, or L1, promote a Markovnikov-selective hydrothiolation in up to 88% yield and >20:1 regioselectivity. Conversely, when smaller bite angle ligands (βn ≤ 86°), for example, dppbz or dppp, are employed, the anti-Markovnikov product is formed in up to 74% yield and >20:1 regioselectivity. Initial mechanistic investigations are performed and are consistent with an oxidative addition/olefin insertion/reductive elimination mechanism for each regioisomeric pathway. We hypothesize that the change in regioselectivity is an effect of diverging coordination spheres to favor either Rh-S or Rh-H insertion to form the branched or linear isomer, respectively.

Original languageEnglish (US)
Pages (from-to)11914-11919
Number of pages6
JournalJournal of the American Chemical Society
Issue number36
StatePublished - Sep 14 2016

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


Dive into the research topics of 'Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines'. Together they form a unique fingerprint.

Cite this