Paul S. Fordred et al.
COMMUNICATIONS
0.82 (3H, obs. t), 0.81 (3H, d, J=6.8 Hz); 13C NMR
(CDCl3): d=151.7, 110.5, 81.5, 32.2, 31.8, 31.5, 29.7, 28.3,
23.0, 20.1, 17.7, 14.5; HR-MS (ESI): m/z=183.1739, calcd.
for C12H24O [MÀ] :183.1749.
[13] D. A. Evans, M. M. Morrissey, J. Am. Chem. Soc. 1984,
106, 3866–3868.
[14] For previous reports of rhodium-catalyzed isomeriza-
tions of exo-methylenic cyclohexanes, exo-methylenic
ketones and exo-methylenic lactones, see: a) P. Stahl,
L. Kissau, R. Mazitschek, A. Huwe, P. Furet, A. Gian-
nis, H. Waldmann, J. Am. Chem. Soc. 2001, 123, 11586–
11593; b) N. De Kimpe, W. Aelterman, Tetrahedron
1996, 52, 12815–12820; c) H. Takayama, R. Sudo, M.
Kitajima, Tetrahedron Lett. 2005, 46, 5795–5797.
[15] A series of other transition metal complexes were un-
successfully screened as catalysts for this isomerization
(E)-2,4-Dimethyldec-4-en-3-ol (7c)
2-Methyl-4-methylenedecan-3-ol (6c) (184 mg, 1 mmol) was
dissolved in MeCN (0.2 mL) and then added via syringe to a
Schlenk tube containing Pd(OH)2/C (125.2 mg, 0.1 mmol
Pd), Cs2CO3 (325.8 mg, 1 mmol) in MeCN (0.8 mL) under
one bar of hydrogen. The reaction mixture was then stirred
at 208C for 40 min, filtered through Celiteꢂ and the solvent
removed under vacuum to afford the title compound.
1H NMR (CDCl3); d=5.38 (1H, t, J=7.1 Hz), 3.59 (1H, d,
J=8.3 Hz), 2.11–1.98 (3H, m), 1.87–1.68 (1H, m), 1.43–1.22
(8H, m), 1.00 (3H, d, J=6.6 Hz), 0.91 (1H, t, J=6.7 Hz),
0.80 (3H, d, J=6.8 Hz); 13C NMR (CDCl3): d=136.6, 128.5,
84.7, 31.9, 31.5, 29.6, 22.9, 19.8, 19.2, 19.1, 14.5, 11.6; HR-MS
(ESI): m/z=207.1732, calcd. for C12H24NaO [M+]: 207.1725.
reaction,
including
Au(PPh3)Cl,
Rh
ACHTUNGRTENN(UNG cod)2OTf,
RhCl3·3H2O, Pd
N
N
2A(PhCN)2.
[16] A mechanism involving a p-allyl palladium intermedi-
ate would be likely to incorporate either one or four
equivalents of deuterium.
[17] See also: a) J. Yu, J. B. Spencer, J. Org. Chem. 1997, 62,
8618–8619; b) J. Yu, P. S. Whitney, J. B. Spencer, J.
Mol. Catal. A 1999, 146, 199–210.
[18] Treatment of trisubstituted allylic alcohol
2 with
3 mol% Pd/C in IPA under a balloon of deuterium gas
for eight hours resulted in 60% incorporation of deute-
rium into its vinylic position.
Acknowledgements
We would like to thank the EPSRC and AstraZeneca for
funding.
[19] Experiments employing <1 bar of hydrogen resulted in
competing oxidation of allylic alcohol 6a to its corre-
sponding ketone.
[20] All syn-/anti-hydrogenated alcohols 8/9 were formed in
a ratio ranging from 1:1 to 2:1, with major isomers un-
assigned.
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Adv. Synth. Catal. 2009, 351, 2310 – 2314