Table 5 Regio- and stereoselectivity of alkyne hydrochalcogenation reactions
NHC catalyst ∆E2 Hydrothiolation (kcal/mol) ∆E2 Hydrothiolation (kcal/mol) ∆E2 Hydrothiolation (kcal/mol) ∆E2 Hydroselenation (kcal/mol) ∆E2 Hydroselenation (kcal/mol) ∆E2 Hydroselenation (kcal/mol)
Markovnikov E-anti-Markovnikov Z-anti-Markovnikov Markovnikov E-anti-Markovnikov Z-anti-Markovnikov
IH 34.08 39.86 26.22 33.44 35.89 24.52
IMe 18.93 22.47 14.71 20.34 20.98 18.15
INH2 20.37 20.98 21.84 17.91 21.02 16.78
ICN 47.24 50.51 * 44.73 48.89 *
IMes# 23.20 26.00 * 17.56 21.37 *
IOH 40.84 41.88 41.80 38.18 39.05 38.01
IOMe 38.14 40.91 37.15 33.79 38.28 37.22
ISH 23.06 27.63 11.42 22.44 29.22 16.11
ISMe 19.78 24.30 9.63 22.88 23.57 14.83
BH 41.37 45.82 36.13 40.09 41.93 33.01
BMe 35.95 40.17 31.41 33.52 36.62 32.33
TH 36.83 40.73 37.45 34.76 40.38 36.73
TMe 38.33 38.32 32.78 35.04 38.58 36.46
PH# 38.47 39.71 31.99 39.05 42.76 38.40
PMe# 34.90 37.64 26.41 31.57 33.17 34.77
# implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES. # implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES. # implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES. # implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES. # implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES. # implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES. # implies values are computed at B3LYP/6-31+G(d) level, * corresponding TSs could not be located on the PES.