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Experimental
General
All reactions were carried out under a nitrogen atmosphere.
Deionised water was degassed by bubbling through a stream of
nitrogen for 30 min prior to use. Reagents were of analytical
grade, and used as obtained from commercial suppliers without
further purification. Compounds 4,25 5a–e, 5h, 5j,26 and 5a-d1
were prepared by methods previously described in the literature.
´
12a
6 (a) V. Cadierno, S. E. Garc´ıa-Garrido, J. Gimeno, A. Varela-Alvarez
and J. A. Sordo, J. Am. Chem. Soc., 2006, 128, 1360–1370; (b) P.
Crochet, J. D´ıez, M. A. Ferna´ndez-Zu´mel and J. Gimeno, Adv.
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and P. Crochet, Green Chem., 2009, 11, 1681–1686; (d) A. E. D´ıaz-
Compounds 5f–g, 5i, 5l–n were used as obtained from supplier.
Flash chromatography was carried out on 60 A (35–70 mm) silica
˚
´
gel. 1H and 13C NMR spectra were recorded at 400 or 500 MHz
and at 100 or 125 MHz, respectively, on a Bruker Advance
spectrometer. Chemical shifts (d) are reported in ppm, using
the residual solvent peaks in CDCl3 (dH 7.26 and dC 77.00) as
internal standard. Coupling constants (J) are given in Hz. High
resolution mass spectra (HRMS) were recorded on a Bruker
microTOF ESI-TOF mass spectrometer.
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Fekete, F. Jo
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Grubbs, Organometallics, 1994, 13, 224–235.
´
7 (a) C. de Bellefon, S. Caravieilhes and E. G. Kuntz, C. R. Acad. Sci.,
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Oberhauser, New J. Chem., 2001, 25, 11–12; (c) D. A. Knight and
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13 U. Ko¨lle, R. Go¨rissen and T. Wagner, Chem. Ber., 1995, 128, 911–
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General procedure for the isomerisation of allylic alcohols in
water
To the allylic alcohol (5, 0.4 mmol or 0.8 mmol) was added
an 8 mM solution of [Rh(COD)(MeCN)2]BF4 (2, 1 or 2 mL,
0.008 mmol or 0.016 mmol, 2 mol%) and PTA (1, 0.016 mmol
or 0.032 mmol, 4 mol%) in water. The reaction was vigorously
stirred (1500 rpm) in a closed tube at room temperature (or the
temperature indicated) for the appropriate time (see Table 3).
The tube was opened, and the reaction mixture immediately
extracted with Et2O (3 ¥ 0.5 mL). If heated, the mixture was
poured onto ice prior to extraction. The reactions were analysed
by TLC and 1H-NMR spectroscopy.
14 (a) For formation of metal hydrides and hydroxides via oxidative
addition of water, see: O. V. Ozerov, Chem. Soc. Rev., 2009, 38, 83–
88; (b) T. Yoshida, T. Okano, Y. Ueda and S. Otsuka, J. Am. Chem.
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15 Joo´ et al. observed formation of Ru-aqua and hydroxide species
with a water soluble Ru–NHC complex: P. Csabai and F. Joo´,
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Acknowledgements
Financial support from the Swedish Research Council
(Vetenskapsra˚det) and from the Berzelius Center Exselent,
Stockholm University is gratefully acknowledged
16 We attribute this partially to the poor solubility of the catalyst in
THF.
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