(a) Reaction scheme of pairwise addition of p-H2 to vinyl
1-13C-pyruvate in CD3OD followed by polarization
transfer to 13C nuclei (HA and HB are two atoms
from the same p-H2 molecule, cat. = [Rh(NBD)(dppb)]BF4).
(b) Reaction scheme of the competing process of norbornadiene hydrogenation with
p-H2. (c) 1H NMR spectrum acquired after 1H
ALTADENA hyperpolarization of ethyl 1-13C-pyruvate with 10 s
p-H2 bubbling duration. (d) Corresponding thermal 1H
NMR spectrum acquired after relaxation of hyperpolarization (multiplied by a
factor of 64). ε1H = 1650, P1H = 5.1% (5.2% at 85%
p-H2 fraction) (calculated using signal 8b+9b). (e)
13C NMR spectrum acquired after 13C hyperpolarization of
ethyl pyruvate (1.1% 13C enrichment) using MFC at 0.025 μT
magnetic field with RG = 203 (p-H2 bubbling duration = 20 s). (f)
13C NMR spectrum of 0.74 M solution of vinyl
1-13C-acetate used as an external reference acquired with RG = 203.
ε13C = 900, P13C = 0.70% (0.88% at 85%
p-H2 fraction). (g) Dependence of conversion of vinyl pyruvate to
ethyl pyruvate on p-H2 bubbling duration (estimated pseudo-first
order rate constant k = 0.035 ± 0.002 s–1). (h)
Dependence of 1H ALTADENA signal (absolute value) of HP ethyl
pyruvate (signal 8b+9b, red squares), norbornene (signal 19d, blue circles) and
norbornane (signal 20b+20d, black triangles) on p-H2 bubbling
duration. (i) Dependence of P1H (at 85% p-H2 fraction) of
ethyl pyruvate (signal 8b+9b, red squares), norbornene (signal 19d, blue
circles) and norbornane (signal 20b+20d, black triangles) on p-H2
bubbling duration. (j) Dependence of P13C (at 85% p-H2
fraction) of ethyl pyruvate on magnetic field used in MFC experiments (data
obtained with the 1.1% 13C-enriched precursor).