TY - JOUR
T1 - Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines
AU - Kennemur, Jennifer L.
AU - Kortman, Gregory D.
AU - Hull, Kami L.
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/14
Y1 - 2016/9/14
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.6b07142
DO - 10.1021/jacs.6b07142
M3 - Article
C2 - 27547858
AN - SCOPUS:84987817747
SN - 0002-7863
VL - 138
SP - 11914
EP - 11919
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -