Chemoselective Oxidation of Allylic and Benzylic Alcohols
FULL PAPERS
acetophenone; 42,755–1 benzophenone; 14,783–4 4,4’-bis(di-
methylamino)benzophenone; C10,281–4 2-cyclohexen-1-
one). GC analysis was performed with an Agilent HP-5 ms
(30 m250 mm0.25 mm) capillary column heated gradually
to 3408C (from 708C, rate 158CminÀ1). Vector gas: He2.
Column head pressure: 7.69 psi.
eralitat Valenciana (Grupos 2003–121 and 842/2005) and
UVEG(UV-AE-20050205) is gratefully acknowledged. N.R
thanks the Spanish Ministerio de Educacion for a fellowship.
We gratefully acknowledge SCSIE (Universidad de Valencia)
for access to the instrumental facilities.
Preparation of Bromomethyl Phenyl Sulfoxide[21]
References
To a solution of methyl phenyl sulfoxide (10 mmol) and an-
hydrous pyridine (22 mmol) in dry acetonitrile (40 mL)
cooled at À408C under an argon atmosphere was added
dropwise a solution of bromine (20 mmol) in dry acetonitrile
(20 mL) at À208C. The mixture was stirred first at À408C
for 1 h and then overnight at room temperature. The solvent
was evacuated in vacuum and the residue was redissolved in
dichloromethane. The organic layer was washed with
Na2S2O3 (0.02 N, 30 mL), dried over anhydrous Na2SO4 and
concentrated to dryness. The crude material was purified by
flash column chromatography (hexane:ethyl acetate 5:1) to
afford the sulfoxide; yield: 80%.1H NMR (·300 MHz,
CDCl3): d=4.16–4.30 (AB, J=12.3 Hz, 2H), 7.50–7.47 (m,
2H) 7.61–7.64 (m, 3H); 13C NMR (·75 MHz, CDCl3): d=
48.8 (t), 124.7 (d), 129.2 (d), 132.0 (d), 141.5 (s); HR-MS
(EI): m/z=217.9363, calcd. for C7H7BrOS (M+): 217.9401.
1-Phenylpentane-1,5-diol (Table 3, entry 2): 1H NMR
(·300 MHz, CDCl3): d=1.80–1.20 (m, 6H), 3.56 (t, J=
5.30 Hz, 2H), 4.61 (dd, J=7.50 and 5.60 Hz, 1H), 7.30–7.20
(m, 5H);. 13C NMR (·75 MHz, CDCl3): d=22.0(t), 32.4(t),
38.7(t), 62.7(t), 74.5(d), 125.8(d), 127.5(d), 128.4(d), 144.7(s);
HR-MS (EI): m/z=180.1157, calcd. for C11H16O2 (M+):
180.1150.
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5-Hydroxy-1-phenylpentan-1-one
(Table 3,
entry 2):
1H NMR (·300 MHz, CDCl3): d=1.80–1.20 (m, 4H), 3.00–
2.90 (m, 2H), 3.70–3.55 (m, 2H), 7.45–7.35 (m, 3H), 7.90–
7.80 (m, 2H); 13C NMR (·75 MHz, CDCl3): d=20.1(t),
32.2(t), 38.1(t), 62.3(t), 128.0(d), 128.5(d), 133.0(d), 136.9(s),
200.4(s); HR-MS (EI): m/z=178.0994, calcd. for C11H14O2
(M+): 178.0995.
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Palladium-Catalyzed Anaerobic Oxidation of
Alcohols; General Procedure
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A mixture of the appropriate alcohol (0.4 mmol), K3PO4
[15] The differences observed in a protic solvent likely arise
from a less pronounced repulsions between the incom-
ing nucleophile and the oxygen of the sulfinyl group
because the solvation.
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[18] Overoxidation does not occur most probably due to
the absence of oxygen and water in the medium.
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(339.6 mg, 1.6 mmol), Pd(OAc)2 (8.9 mg. 0.04 mmol) and
A
racemic BINAP (12.4 mg, 0.02 mmol) was loaded in a
Schlenk reaction tube. The mixture was degassed by alterna-
tive vacuum and argon purge cycles. a-Bromo sulfoxide
(86.8 mg, 0.4 mmol) and THF (4 mL) were added and the
mixture was heated at 658C for 12 h. The reaction mixture
was taken up in ether (20 mL) and washed with a saturated
NH4Cl aqueous solution and brine. The organic phase was
dried over MgSO4, filtered, and concentrated under vacuum.
The crude product was purified by column chromatography
on silica gel to afford the corresponding carbonyl com-
pound.
Acknowledgements
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Chem. 1982, 236, 61.
Financial support by the Spanish Dirección General de In-
vestigación Científica y TØcnica (BQU2003–00315), the Gen-
[21] M. Cinquini, S. Colonna, J. Chem. Soc., Perkin Trans. 1
1972, 1883.
Adv. Synth. Catal. 2007, 349, 987 – 991
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
991