P. L. Alsters, J.-M. Aubry et al.
FULL PAPER
7
1 mmol), a solution of geranylamine (1d, 1.85 mL, 10 mmol) and aqueous
Experimental Section
HNO
was stirred overnight at 308C, during which it turned light yellow. A
concentrated aqueous Na SO solution (30 mL) was added to the mixture,
3
(65%, 0.69 mL, 10 mmol) in MeOH (5 mL) was added. The mixture
Reagents: Lanthanum oxide La
La(OH) (99.9%), lanthanum nitrate La(NO
num chloride LaCl ¥ 7 H O (99.9%), sodium molybdate Na
99%), sodium hydroxide (99.99%), geranylamine (90%), b-citronellol
95%), a-terpinene (85%), and tiglic acid (98%) were purchased from
2
O
3
(99.99%), lanthanum hydroxide
¥ 6H O (99.99%), lantha-
MoO ¥ 2H
2
3
3
3
)
3
2
which was then stirred for one hour, saturated with NaCl, and extracted
3
2
2
4
2
O
with ethyl acetate (5 Â 50 mL). The combined organic layers were dried
(
(
over Na
2
SO
4
and the solvent was removed on the rotary evaporator to leave
1
a yellow oil (1.21 g). H NMR spectroscopy showed that this oil was a
mixture of the substrate 1d, the two isomers of the product (secondary 2d
and tertiary 2d' alcohols), and some traces of impurities (ratio according to
Aldrich Chemie. Hydrogen peroxide (50% Rectapur) and hydrochloric
acid (37% Normapur) were obtained from Prolabo. 4-Methyl-pent-3-en-2-
ol was prepared according to literature procedures[30] and sodium tiglate
1
H NMR: 1d/2d/2d' 28:29:43, according to GC: 28:27:45). Separation by
was obtained from tiglic acid by addition of one equivalent of NaOMe in
column chromatography (eluent: CH
0:5:1) yielded substrate 1d (0.20 g) as a yellow oil and a light yellow oil
0.65 g) containing the products (mixture of isomers; 2d/2d' 41:59). The
2 2 3
Cl /MeOH/aqueous NH (25%)
methanol.
3
(
1
Instrumentation: IR detector: The IR emission of O
2
was measured with a
liquid nitrogen-cooled germanium photodiode detector (Model EO-817L,
North Coast Scientific Co., Santa Rosa, CA, USA) sensitive in the spectral
assignment of the two isomeric amino alcohols is based on the relative
intensities of the signals and on a comparison of the NMR data of the
oxidized double bond region with the NMR data of that region in the
isomeric products obtained from b-citronellol. Yield: 0.65 g (38%).
H
2
region from 800 to 1800 nm, with a 0.25 cm detector and a sapphire
[
31]
1
2
window. The emission spectrum of O was recorded with a calibrated
FT-Raman instrument (Bruker FRA 106 FT-Raman module adapted to an
IFS 88 FTIR bench; LASIR, USTL, Villeneuve d×Ascq, France) operating
with a similar germanium diode detector.
1
CC(Me)CH(OH)CH
CH
C(Me)CHCH
NH
(2d): H NMR (CDCl
,
2
2
2
2
2
3
3
00 MHz, 258C): d 5.22 (overlap;CH), 4.88 (s, 1H;CHH), 4.77 (s, 1H;
CHH), 3.97(t, J 6.8 Hz, 1H; CHOH), 3.22 (overlap; NCH ), 2.0 (b, 5H;
2
Typical luminescence experiment: An aqueous solution (30 mL H
2
O)
OH NH CCH ), 1.66 (s, 3H; CH ), 1.60 (overlap; C(OH)CH ),
2
2
3
2
containing La(NO ¥ 6H O (1.7g, 0.1 m, 4 mmol) was maintained at 258C
3
)
3
2
1.58 ppm (s, 3H; CH ); 13C {
1
H} NMR (CDCl , 75.5 MHz, 258C): d 149.4
3
3
and circulated, with the aid of a peristaltic pump, through a quartz cell
positioned in front of the germanium detector. When the background noise
(Cquat), 137.4 (Cquat), 127.7 (CH ), 112.8 (CH), 77.1 (HOCH), 41.2
2
(NCH ), 37.3 (CCH ), 34.8 (HOCCH ), 19.4 (CH ), 18.0 ppm (CH ).
2
2
2
3
3
of the IR signal was stabilized, H
2
O
2
(50%, 5.7mL, 2.5 m, 100 mmol) was
1
Me
2
C(OH)CHCHCH
2
C(Me)CHCH
2
NH
2
(2d'):
H
3
NMR (CDCl ,
introduced. The pH was rapidly adjusted to 9.0 by addition of NaOH (5m)
and the total volume of the solution was adjusted to 40 mL by addition of
3
3
00 MHz, 258C): d 5.4 ± 5.6 (m, 2H; CHCH), 5.22 (overlap; CH),
.22 (overlap; NCH ), 1.59 (s, 3H; CH ),
), 2.63 (d, J 6.4 Hz, 2H; CCH
.25 ppm (s, 6H; 2 Â CH , 75.5 MHz, 258C): d
2
2
3
H
2
O (3 mL). The pH of the reaction medium was kept constant during the
reaction by addition of small amounts of concentrated HCl or NaOH. The
intensity of the luminescence signal (I ) was recorded, and simultaneously,
13
1
1
1
3 3
); C { H} NMR (CDCl
41.6 (CH), 138.5 (Cquat), 127.2 (CH), 126.4 (CH), 72.4 (HOC), 43.9
D
CCH
(
2
), 41.2 (NCH
2
), 31.6 (C(CH
20NO] 170.1545, found 170.1568.
3
)
2
), 18.0 ppm (CH
3
).
1
mL of the reaction medium was added to H
2
SO
4
(10 mL, 1m), and H
2
O
O
2
HRMS calcd for [C10
H
was titrated with KMnO
4
(0.04m) to monitor the evolution of the H
2
2
concentration during the reaction.
Oxidation experiments
Oxidation of b-citronellol (1b): A solution of La(NO
3
)
3
¥ 6H
2
O (65 mg,
Acknowledgement
0
.15 mmol) and b-citronellol (1b, 0.92 mL, 5.0 mmol) in MeOH (8 mL) was
warmed to 308C, after which aqueous H (50%, 3.3 mL, 58 mmol) and
aqueous NaOH (5m, 90 mL, 0.45 mmol) were added. A white, milky
suspension was formed, and this was stirred overnight at 308C. The MeOH
2
O
2
Financial support by DSM is gratefully acknowledged. We thank B.
Sombret (LASIR) for his technical support with the Raman FT spectrom-
eter.
was removed on the rotary evaporator and H
white suspension was extracted with Et
O (5 Â 30 mL) and the combined
Et O layers were dried over Na SO . After filtration, the Et O was
removed in vacuum to leave a colorless oil containing the starting material
2
O (30 mL) was added. The
2
2
2
4
2
[
[
1] J. M. Aubry, J. Am. Chem. Soc. 1985, 107, 5844 ± 5849.
2] J. M. Aubry, B. Cazin, Inorg. Chem. 1988, 27, 2013 ± 2014.
1
5
b (7%) and the two isomers of the hydroperoxides of b-citronellol (2b/2b'
5:45), according to 1H NMR spectroscopy. The chemical shifts of the
[3] V. Nardello, J. Marko, G. Vermeersch, J. M. Aubry, Inorg. Chem. 1995,
34, 4950 ± 4957.
[
32]
products are in accordance with literature values. Yield: 0.82 g (87%).
[
4] V. Nardello, S. Bouttemy, J. M. Aubry, J. Mol. Catal. A: Chemical,
997, 117, 439 ± 447.
Oxidation of a-terpinene (1a): The oxidation of a-terpinene (1a, 0.81 mL,
1
5
0
mmol) was performed similarly to that of b-citronellol (1b), but now with
.6 mmol of NaOH. A light yellow oil was obtained after workup. H NMR
[5] J. M. Aubry, B. Cazin, F. Duprat, J. Org. Chem. 1989, 54, 726 ± 728.
[6] J. M. Aubry, S. Bouttemy, J. Am. Chem. Soc. 1997, 119, 5286 ± 5294.
[7] V. Nardello, K. Briviba, H. Sies, J. M. Aubry, Chem. Commun. 1998,
1
spectroscopy showed this oil to contain ascaridole 2a, together with 9% of
p-cymene (impurity in the a-terpinene starting material). The chemical
shifts of the product are in accordance with literature data. Yield: 0.63 g
5
99 ± 600.
8] V. Nardello, J. Marko, G. Vermeersch, J. M. Aubry, Inorg. Chem. 1998,
7, 5418 ± 5423.
9] V. Nardello, J. M. Aubry, T. Linker, Photochem. Photobiol. 1999, 70,
24 ± 530.
[
[
[
23b]
(
74%).
Oxidation of 4-methyl-pent-3-en-2-ol (1c): A solution of La(NO
217mg, 0.5 mmol) in H O (2 mL) was warmed to 308C, after which
aqueous H (50%, 8.5 mL, 150 mmol), aqueous NaOH (10m, 150 mL,
.5 mmol), and 4-methyl-pent-3-en-2-ol (1c, 0.51 g, 5 mmol) were added. A
white, milky suspension was formed, and this was stirred for 48 h at 308C.
Na SO (5 g, 40 mmol) was added to the mixture. The mixture was stirred
for one hour, saturated with NaCl, and extracted with ethyl acetate (5 Â
0 mL). The combined organic layers were dried over Na SO . After
3
3 3 2
) ¥ 6H O
(
2
5
2
O
2
[
10] C. Pierlot , V. Nardello, J. Schrive, C. Mabille, J. Barbillat, B. Sombret,
J. M. Aubry, J. Org. Chem. 2002, 67, 2418 ± 2423.
11] K. Bˆhme, H. D. Brauer, Inorg. Chem. 1992, 31, 3468 ± 3471.
12] Q. Niu, C. S. Foote, Inorg. Chem. 1992, 31, 3472 ± 3476.
13] F. Van Laar, D. E. De Vos, D. Vanoppen, B. Sels, P. A. Jacobs, A.
Del Guerzo, F. Pierard, F. K. Kirsch-De Mesmaeker, Chem. Commun.
1
[
[
[
2
3
3
2
4
filtration, the ethyl acetate was removed in vacuum to afford a colorless oil,
containing 4-methyl-pent-4-ene-2,3-diol (2c, erythro/threo 4:1) together
with ꢀ5% of the epoxide 2c' (erythro/threo 1:4). The chemical shifts of the
diol and epoxide products are in accordance with literature data.[
Yield: 0.36 g (60%).
1
998, 267± 268.
[
14] B. F. Sels, D. E. De Vos, P. J. Grobet, F. Pierard, F. K. Kirsch-
De Mesmaeker, P. A. Jacobs, J. Phys. Chem. B. 1999, 103, 11114 ±
27b, 33]
1
1123.
[
15] B. F. Sels, D. E. De Vos, P. J. Grobet, P. A. Jacobs, Chem. Eur. J. 2001,
7, 2547± 2556.
[16] B. F. Sels, D. E. De Vos, P. A. Jacobs, Catal. Rev. 2001, 43, 443 ± 488.
Oxidation of geranylamine (1d): A solution of La(NO
.5 mmol) in MeOH (5 mL) was warmed to 308C, after which aqueous
NaOH (10m, 100 mL, 1.0 mmol) was added. The resulting white suspension
was stirred for one minute. After addition of aqueous H (50%, 4 mL,
3 3 2
) ¥ 6H O (217mg,
0
[17] D. E. De Vos, J. Wahlen, B. F. Sels, P. A. Jacobs, Synlett, 2002, 367±
2
O
2
380.
440
¹ 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Chem. Eur. J. 2003, 9, No. 2