R. West et al.
1
sulfate. Some of aldehyde 5c was chromatographed (DCM) for 15.88, 11.89, 11.85; MS (EI) m/z 416 (M , 46.4%), 280 (13.7%), 165
identification, and the remainder was used crude in the next (39.1%), 151 (100%), 75 (70.0%).
1
= 0.68 (DCM), H NMR (CDCl
step. Clear yellow oil, R
f
3
) d 9.75 (t,
1
H, CHO, J = 1.85 Hz), 6.38 (s, 1H, Ar-H), 5.16 (overlapping
triplets, 2H, C = CH), 2.70 (t, 2H, C-4 H), 2.52 (t, 2H), 2.33 (t, 2H),
.18 (m, 1H, C-3 H), 2.13 (overlapping singlets, 6H, Ar-CH ), 2.08
2
3
(
m, 4H), 1.80 (m, 4H), 1.63 (s, 3H, CH ), 1.61 (s, 3H, CH ), 1.45 (s, References
3
3
1H, C-3 H),1.30 (s, 3H, C-2 CH
CH
1
3
1
3
3
), 1.04 (s, 9H, 3 CH
3
), 0.21 (s, 6H, 2
1
); C NMR (CDCl
3
3
3
) d 202.57, 146.10, 145.82, 134.68, 132.91,
26.15, 125.61, 125.36, 124.67, 117.66, 115.81, 75.11, 42.15,
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1
6.09, 15.83, 12.87, 12.07, ꢀ4.22; MS (EI) m/z 498 (M , 99.3%),
62 (60.2%), 265 (267.0%), 73 (100%).
[
[
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3
3,13,13-trideutero-4,8-dimethyl-12-trideuteromethyl-trideca-
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[
[
Phosphonium salt 6 (207 mg, 0.53 mmol) was dissolved in dry
THF (10 mL) under an argon atmosphere and lithium bis(tri-
methylsilyl)amide (1.0 M in THF, 1.3 mL, 1.3 mmol) was added
dropwise. The solution of ylide was stirred for 1 h, then a
solution of crude aldehyde 5c (228 mg, 0.46 mmol) dissolved in
dry THF (5 mL) was slowly added via cannula. After 15 h, the
reaction mixture was quenched with ammonium chloride
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(
10 mL) and 7c was purified via column chromatography
(
DCM) (99.7 mg, 0.19 mmol, 36% for two steps), pale yellow oil, [11] C. K. Sen, S. Khanna, S. Roy, Mol. Aspects. Med. 2007, 28, 692–728.
1
DOI:10.1016/j.mam.2007.03.001.
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R = 0.82 (DCM), H NMR (CDCl ) d 6.39 (Ar-H), 5.16 (overlapping
triplets, 3H, C = CH), 2.72 (t, 2H, C-4 H), 2.18 (m, 2H, C-2 H), 2.14
f
3
[
0
1991, 10, 263–275.
(
CH ), 1.79,1.76 (m, 2H, C-3 H), 1.70 (s, 3H, CH ), 1.62,1.57 (m, 2H,
s, 6H, Ar-CH ), 2.10 (m, 4H, CH ), 2.04 (m, 4H, CH
3
2
2
), 1.81 (m, 2H, [13] Y. J. Suzuki, M. Tsuchiya, S. R. Wassall, Y. M. Choo, G. Govil, V. E.
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2
3
[
C-1 H), 1.64 (s, 6H, 2 CH
CH ), 0.22 (s, 6H, 2 CH ); C NMR (CDCl ) d 146.10, 145.84,
3 3 3
3
3
), 1.30 (s, 3H, C-2 CH ), 1.05 (s, 9H, 3
1
3
1994, pp. 354–366.
1
1
2
1
35.05, 134.95, 131.04, 126.17, 125.65, 125.53, 124.42, 124.23,
17.66, 115.79, 75.14, 39.85, 39.75, 39.72, 31.53, 30.34, 29.73,
6.76, 26.62, 25.89, 24.05, 22.44, 22.24, 18.27, 16.02, 15.88, 12.86, [16] C. Suarna, R. L. Hood, R. T. Dean, R. Stocker, Biochim. Biophys. Acta
1
2.05, -4.24; MS (EI) m/z 530 (M , 28.0%), 394 (82.0%), 262
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[
(
84.3%), 183 (67.8%), 43 (100%).
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(
R)-2,7,8-trimethyl-2-((3E,7E)-13,13,13-trideutero-4,8-dimethyl-12-
trideuteromethyl-trideca-3,7,11-trienyl)-chroman-6-ol (8c)
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c (176 mg, 0.33 mmol) was dissolved in dry THF (5 mL) and [20] F. Gu, T. Netscher, J. Atkinson, J. Labelled Compds. Radiopharm.
1
7
2
006, 49, 733–743. DOI:10.1002/jlcr.1090.
tetrabutylammonium fluoride (1.0 M in THF, 1.7 mL, 1.7 mmol)
was added dropwise. The solution was stirred at room
temperature for 2 h and then quenched with 1 N HCl (2.5 mL).
Product 8c was purified via column chromatography (DCM/
[
[
[
[
21] B. C. Pearce, R. A. Parker, M. E. Deason, A. A. Qureshi, J. J. Wright,
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hexane 3:1). Pale yellow oil (101 mg, 0.24 mmol, 73%), R
1
f
= 0.25
DCM/hexane, 3:1); H NMR (CDCl ) d 6.39 (Ar-H), 5.11 (over-
(
lapping triplets, 3H, C = CH), 2.72 (t, 2H, C-4 H), 2.18 (m, 2H, C-2
3
24] E. A. Couladouros, V. I. Moutsos, M. Lampropoulou, J. L. Little, J. A.
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0
H), 2.15 (s, 3H, Ar-CH
3
), 2.14 (s, 3H, Ar-CH
3
), 2.10 (m, 4H, CH
), 1.62 (s, 3H, CH
.61(s, 3H, CH ), 1.65,1.59 (m, 2H, C-1 CH ), 1.28 (s, 3H, C-2 CH );
2
), [25] K. M. Chen, J. E. Semple, M. M. Joullie, J. Org. Chem. 1985, 50,
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),
3997–4005.
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[
1
3
2
3
1
3
3
C NMR (CDCl ) d 146.27, 145.70, 135.08, 134.97, 125.81, 124.43,
[
[
27] E. E. van Tamelen, R. G. Nadeau, Bioorg. Chem. 1982, 11, 197–218.
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124.35, 124.19, 121.62, 118.24, 112.13, 77.21, 75.22, 39.79, 39.72,
39.69, 31.41, 29.42, 26.74, 26.60, 25.61, 23.99, 22.28, 22.21, 15.99,
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