Samarium Diiodide Mediated Ketyl–Aryl Coupling
(tq, J = 4.1, 13.4 Hz, 1 H, 6-H), 1.57 (br. s, 1 H, OH), 1.61 (dt, J
= 4.5, 13.4 Hz, 1 H, 7-H), 1.74 (ttd, J = 2.2, 4.5, 13.4 Hz, 1 H, 6-
H), 1.83 (dddd, J = 1.5, 2.3, 4.1, 13.4 Hz, 1 H, 7-H), 1.95 (tdt, J ≈
2, 4.5, 13.4 Hz, 1 H, 5-H), 2.14 [s, 3 H, O(C=O)CH3], 2.23 (tdd, J
= 2.2, 4.1, 13.4 Hz, 1 H, 5-H), 2.75–2.79 (m, 2 H, 3-H), 2.88 (dt, J
= 3.5, 7.6 Hz, 1 H, 8a-H), 5.41 (tt, J = 1.7, 3.5 Hz, 1 H, 4-H), 5.56
(td, J = 1.7, 3.5 Hz, 1 H, 1-H) ppm. 13C NMR (126 MHz, CDCl3):
δ = 21.0, 21.7 (2q, CH3), 24.0 (t, C-6), 28.2 (t, C-3), 34.0 (t, C-5),
41.5 (t, C-7), 50.2 (d, C-8a), 74.5 (s, C-8), 111.9 (d, C-1), 116.8 (d,
C-4), 135.6 (s, C-4a), 147.2 (s, C-2), 169.3 (s, C=O) ppm. IR (film):
2.20 mmol), H M PA (3.2 mL, 3.2 g, 18 mmol), 35 (0.204 g,
1.00 mmol), tBuOH (0.19 mL, 0.15 g, 2.0 mmol) and THF (50 mL
+ 25 mL) afforded after purification by flash-chromatography on
silica gel (hexane/ethyl acetate, 19:1Ǟ9:1) compound 36a (0.074 g,
36%) and compound 36b (0.017 g, 8%) as colourless oils.
1
36a: H NMR (500 MHz, CDCl3): δ = 1.15 (s, 3 H, 1-CH3), 1.48
(br. s, 1 H, OH), 1.53–1.94 (m, 6 H, CH2), 2.23 (s, 3 H, COCH3),
2.31 (dd, J = 5.4, 19.5 Hz, 1 H, 10-H), 2.73 (dd, J = 4.4, 19.5 Hz,
1 H, 10-H), 5.55 (d, J = 10.2 Hz, 1 H, 6-H), 6.37 (dd, J ≈ 1, 10.2 Hz,
1 H, 7-H), 6.81 (mc, 1 H, 9-H) ppm. 13C NMR (126 MHz, CDCl3):
δ = 18.9 (t, CH2), 23.4, 25.2 (2q, CH3), 30.0 (t, C-10), 38.6* (2t,
CH2), 48.4 (s, C-5), 83.0 (s, C-1), 119.6 (d, C-6), 133.6 (d, C-7),
135.6 (s, C-8), 138.4 (d, C-9), 196.8 (s, C=O) ppm. *Signal has
ν = 3435 (O–H), 3045–2835 (= C–H, C–H), 1755 (C= O), 1670
˜
(C=C) cm–1. HRMS (ESI): C13H18NaO3: calcd. 245.1154; found
245.1169.
rac-(8S,8aS)-(8-Hydroxy-8-methyl-3,5,6,7,8,8a-hexahydronaphtha- higher intensity.
len-2-yl)methanesulfonate (31): According to the general procedure,
1
36b: H NMR (500 MHz, CDCl3): δ = 1.15 (s, 3 H, 1-CH3), 1.38
samarium (0.140 g, 0.930 mmol), iodine (0.213 g, 0.840 mmol),
H M PA (0.98 mL, 1.0 g, 5.6 mmol), 30 (0.080 g, 0.31 mmol),
tBuOH (0.07 mL, 0.06 g, 0.8 mmol) and THF (20 mL + 10 mL)
afforded after purification by flash-chromatography on silica gel
(hexane/ethyl acetate, 8:1Ǟ1:1) compound 31 (0.045 g, 56%) as a
colourless oil. 1H NMR (500 MHz, CDCl3): δ = 1.09 (s, 3 H, CH3),
1.36 (tq, J = 4.1, 13.5 H z, 1 H , 6-H ), 1.63 (ddt, J = 0.7, 4.1,
13.1 Hz, 1 H, 7-H), 1.72–1.80 (m, 2 H, 6-H, OH), 1.84 (mc, 1 H,
7-H), 1.95 (mc, 1 H, 5-H), 2.24 (tdd, J = 2.1, 4.2, 13.4 Hz, 1 H, 5-
H), 2.89–2.96 (m, 3 H, 3-H, 8a-H), 3.13 [s, 3 H, O(SO2)CH3], 5.40–
5.42 (m, 1 H , 4-H ), 5.85–5.87 (m, 1 H , 1-H ) ppm. 13C N M R
(126 MHz, CDCl3): δ = 22.0 (q, CH3), 23.8 (t, C-6), 29.3 (t, C-3),
33.9 (t, C-5), 38.0 [q, O(SO2)CH3], 41.7 (t, C-7), 50.5 (d, C-8a),
74.4 (s, C-8), 114.4 (d, C-1), 116.7 (d, C-4), 135.4 (s, C-4a), 147.0
(br. s, 1 H, OH), 1.54–1.90 (m, 6 H, CH2), 2.25 (s, 3 H, COCH3),
2.31 (dd, J = 4.9, 18.8 Hz, 1 H, 10-H), 2.46 (dd, J = 4.6, 18.8 Hz,
1 H, 10-H), 5.85 (d, J = 10.2 Hz, 1 H, 6-H), 6.56 (dd, J = 1.4,
10.2 Hz, 1 H, 7-H), 6.72 (mc, 1 H, 9-H) ppm. 13C NMR (126 MHz,
CDCl3): δ = 19.1 (t, CH2), 23.5, 25.2 (2q, CH3), 32.7 (t, C-10), 36.8
(t, CH2), 38.0 (t, CH2), 47.9 (s, C-5), 83.4 (s, C-1), 121.7 (d, C-6),
132.3 (d, C-7), 136.1 (s, C-8), 136.9 (d, C-9), 196.4 (s, C=O) ppm.
The relative configurations or 36a and 36b were assigned by com-
parison with the literature known compound 34. Due to the low
stability of 36a/36b and their rapid decomposition no further char-
acterization was possible.
rac-(4R,4aS,5S)-5-Hydroxy-4-(1-hydroxy-1-methylethyl)-5-methyl-
4,4a,5,6,7,8-hexahydronaphthalene-2-carbonitrile (37): According to
the general procedure, but without tBuOH. Samarium (0.361 g,
2.40 mmol), 1,2-diiodoethane (0.620 g, 2.20 mmol), H M PA
(3.2 mL, 3.2 g, 18 mmol), 21 (0.187 g, 1.00 mmol), and TH F
(50 mL) afforded a solution which was treated with acetone
(0.290 g, 5.00 mmol) in THF (25 mL) after 5 min. Purification by
flash-chromatography on silica gel (hexane/ethyl acetate, 9:1Ǟ1:1)
furnished compound 37 (0.130 g, 53%) as a colourless solid; m.p.
(s, C-2) ppm. IR (film): ν = 3420 (O–H), 3030–2835 (=C–H, C–
˜
H), 1660 (C=C) cm–1. MS (EI, 80 eV, 60 °C): m/z (%) = 258 (43)
[M+], 240 (24), 238 (100), 200 (23), 198 (25), 161 (80), 159 (54), 131
(17), 121 (29), 120 (20), 91 (21), 85 (18). HRMS: C12H18O4S: calcd.
258.09259; found 258.09210.
5-Phenylpentan-2-one (9): According to the general procedure, sa-
marium (0.079 g, 0.52 mmol), iodine (0.118 g, 0.465 mmol), HMPA
(0.55 mL, 0.56 g, 3.1 mmol), 32 (0.079 g, 0.17 mmol), tBuOH
(0.04 mL, 0.03 g, 0.4 mmol) and THF (20 mL + 10 mL) afforded
after purification by flash-chromatography on silica gel (hexane/
ethyl acetate, 8:1Ǟ2:1) compound 9 (0.021 g, 76%) as a pale yel-
1
106–110 °C. H NMR (500 MHz, CDCl3): δ = 1.03, 1.05, 1.34 (3s,
3 H each, CH3), 1.44 (mc, 1 H, 7-H), 1.68 (dt, J = 4.2, 12.9 Hz, 1
H, 6-H), 1.81–1.86 (m, 1 H, 7-H), 1.89 (br. d, J ≈ 13 Hz, 1 H, 6-
H), 2.03 (dt, J = 4.6, 12.9 Hz, 1 H, 8 H), 2.17 (br. s, 1 H, OH),
2.27 (mc, 1 H, 8-H), 2.31 (br. s, 1 H, OH), 2.61–2.63 (m, 1 H, 4a-
H), 2.75 (t, J = 5.0 Hz, 1 H, 4-H), 5.60 (s, 1 H, 1-H), 6.31 (d, J =
5.0 Hz, 1 H, 3-H) ppm. 13C NMR (126 MHz, CDCl3): δ = 20.5 (q,
CH3), 24.1 (t, C-7), 24.2, 29.0 (2q, CH3), 34.7 (t, C-8), 42.7 (t, C-
6), 45.1 (d, C-4), 47.1 (d, C-4a), 77.0 (s, C-C-4), 77.3 (s, C-5), 110.9
(s, C-2), 112.8 (d, C-1), 118.8 (s, CN), 138.3 (d, C-3), 142.8 (s, C-
1
low oil. H NMR (500 MHz, CDCl3): δ = 1.91 (quint, J = 7.5 Hz,
2 H, 4-H), 2.12 (s, 3 H, 1-H), 2.44 (t, J = 7.5 Hz, 2 H, 3-H), 2.62
(t, J = 7.5 Hz, 2 H, 5-H), 7.15–7.21 (m, 3 H, Ar), 7.26–7.30 (m, 2
1
H, Ar) ppm. The H NMR spectroscopic data are in accordance
with those given in the literature.[34]
rac-(1S,5S)-Methyl 1-Hydroxy-1-methylspiro[4.5]deca-6,8-diene-8- 8a) ppm. IR (KBr): ν = 3440 (O–H), 3055–2865 (=C–H, C–H),
˜
carboxylate (34): According to the general procedure, samarium
(0.180 g, 1.20 mmol), 1,2-diiodoethane (0.310 g, 1.10 mmol),
H M PA (1.6 mL, 1.6 g, 9.0 mmol), 33 (0.110 g, 0.500 mmol),
tBuOH (0.095 mL, 0.074 g, 1.00 mmol) and THF (25 mL + 13 mL)
afforded after purification by flash-chromatography on silica gel
(hexane/ethyl acetate, 9:1Ǟ7:3) compound 34 (0.064 g, 58%) as
colourless oil. 1H NMR (500 MHz, CDCl3): δ = 1.19 (s, 3 H, 1-
CH3), 1.47 (br. s, 1 H, OH), 1.50–1.93 (m, 6 H, CH2), 2.31 (dd, J
= 5.2, 19.4 Hz, 1 H, 10-H), 2.69 (dd, J = 4.3, 19.4 Hz, 1 H, 10-H),
3.71 (s, 3 H, OCH3), 5.55 (dd, J = 0.7, 10.0 Hz, 1 H, 6-H), 6.37
(dd, J = 1.5, 10.0 Hz, 1 H, 7-H), 6.91 (mc, 1 H, 9-H) ppm. The 1H
NMR spectroscopic data are in accordance with those given in the
literature.[25]
2225 (CN), 1600 (C=C) cm–1. C15H21NO2 (247.3): calcd. C 72.84,
H 8.56, N 5.66; found C 72.24, H 8.56, N 5.78.
rac-Ethyl (4R,4aS,5S)-5-Hydroxy-4-(1-hydroxy-1-methylethyl)-5-
methyl-4,4a,5,6,7,8-hexahydronaphthalene-2-carboxylate (38): Ac-
cording to the general procedure, but without tBuOH. Samarium
(0.361 g, 2.40 mmol), 1,2-diiodoethane (0.620 g, 2.20 mmol),
HMPA (3.2 mL, 3.2 g, 18 mmol), 23 (0.234 g, 1.00 mmol) and THF
(50 mL) afforded a solution, which was treated with acetone
(0.290 g, 5.00 mmol) in THF (25 mL) after 5 min. Purification by
flash-chromatography on silica gel (hexane/ethyl acetate, 9:1Ǟ7:3)
provided compound 38 (0.224 g, 76%) as a colourless solid; m.p.
1
127–130 °C. H NMR (500 MHz, CDCl3): δ = 0.99, 1.02 (2 s, 3 H
each, CH3), 1.29 (t, J = 7.1 Hz, 3 H, OCH2CH3), 1.36 (s, 3 H,
rac-1-(1S,5S)- and 1-[(1R,5S)-1-Hydroxy-1-methylspiro[4.5]deca- CH3), 1.34–1.49 (m, 1 H, 7-H), 1.68 (dt, J = 4.3, 13.2 Hz, 1 H, 6-
6,8-dien-8-yl]ethanone (36a and 36b): According to the general pro-
cedure, samarium (0.361 g, 2.40 mmol), 1,2-diiodoethane (0.620 g,
H), 1.75–1.81 (m, 1 H, 7-H), 1.86 (br. d, J ≈ 13 Hz, 1 H, 6-H), 2.01
(dt, J = 4.9, 12.9 Hz, 1 H, 8-H), 2.29 (br. d, J ≈ 13 Hz, 1 H, 8-H),
Eur. J. Org. Chem. 2008, 3635–3646
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
3643