d 209.4 (C), 62.2 (CH2), 40.5 (CH2), 30.0 (CH3), 26.5 (CH2). MS-
Notes and references
ESI+: [M-H2O+H]+ calcd for C5H10O2 85.0648; found 85.0656.
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5-(2-Methyl-tetrahydrofuran-2-yloxy)pentan-2-one (9¢). The
product was directly obtained following the standard procedure
using the catalyst indicated in Scheme 3 as yellow oil (after 2
days, 22% yield) without further purification. 1H NMR (500 Hz,
CDCl3) d 3.84–3.80 (m, 1H), 3.78–3.74 (m, 1H), 3.39 (dt, J = 9.3,
6.4 Hz, 1H), 3.33 (dt, J = 9.3, 6.1 Hz, 1H), 2.42 (t, J = 7.4 Hz,
1H), 2.40 (t, J = 7.2 Hz, 1H), 2.08 (s, 3H), 1.98–1.90 (m, 2H),
1.85–1.81 (m, 1H), 1.73 (tt, J = 7.3, 6.3 Hz, 2H), 1.66–1.63 (m,
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C10H18NaO3 209.1148; found 209.1154.
Pent-3-en-1-ol (11). The product was directly obtained follow-
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the catalyst indicated in Scheme 3 as yellow oil inseparable from 9
and 9¢ without further purification (12 mg, 59% yield). 1H NMR
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(t, J = 6.5 Hz, 2H), 2,27 (dt, J = 6.5, 1.1 Hz, 1H), 2,24 (dt, J = 6.5,
1.1 Hz, 1H), 1.69 (d, J = 6.3 Hz, 3H). 13C NMR (75 MHz, CDCl3)
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General Procedure used for the samples in the kinetic studies
The sample for the kinetic studies was prepared as follows: an
aqueous solution of 4-pentynoic acid was added to another aque-
ous solution of cis-PtCl2(15N-NHMe2)2. The mixture was prepared
using the ratios: [H2O]/[D2O] = 90 : 10, platinum concentration =
2.5 mM and acid/Pt = 100 : 1. The time-dependent transformation
1
of the mixture at 298 K was monitored by 1D H and 2D [1H,
15N] HSQC NMR spectroscopy. NMR spectra were recorded on a
Bruker DRX-500 spectrometer (1H 500.13 MHz, 15N 50.68 MHz).
1
The H and 15N chemical shift were relative to TSP and liquid
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22 The amount of speciation has been calculated from the total area of
the crosspeaks in each spectrum. The titration was also performed in
this sample and did not affect the new signals v and vi, which indicates
that those species are obviously not aqua species.
23 The free dimethylamine peak can already be detected after 5 h of
reaction but as a minor product (4% compared to 43% of the aqua
species). The free amine signal became important with the first sign of
a second reaction observed in this catalytic study: the opening of the
cyclation affording a new acid where the alkyne moiety is transformed
into a ketone (observed in the 1H NMR, Fig. 2 from 10 h on, compound
starred in the spectra).
ammonia respectively. All NMR data were analyzed with the
TopSpin program (Bruker). pH values were determined using a
Metrohm 744 pH meter. The meter was calibrated using pH buffers
at pH 7.00 and 4.01. Adjustments in pH for the titration were made
at 6 and 10 using 0.1 and 0.01 M NaOH.
Acknowledgements
This work was made possible by the Ministerio de Educacio´n
y Ciencia (grant SAF2009-09431), which is gratefully acknowl-
edged. The Ministerio de Ciencia e Innovacio´n is thanked for
a Ramo´n y Cajal contract (J. A.) and a pre-doctoral fellowship
(V. S.).
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