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1
1705, 1612, 1512 cmꢃ1; H NMR d 0.85 (s, 3H), 1.27 (s, 3H), 1.42–1.53 (m,
1H), 1.60–1.69 (m, 1H), 1.78–1.94 (m, 2H), 1.99–2.07 (m, 1H), 2.02 (d, 3H,
J
C,H=126.8 Hz), 2.81 (dd, 1H, J=10.0, 7.2 Hz), 3.32–3.41 (m, 2H), 3.80
(s, 3H), 4.41 (s, 2H), 6.87 (m, 2H), 7.25 (m, 2H); 13C NMR d 17.2, 23.0,
30.1, 30.4, 30.8, 38.9, 43.2, 54.3 (d, JC,C = 13.6 Hz), 55.2, 68.2, 72.5, 113.7,
2
1
129.2, 130.5, 159.1, 208.0 (d, JC,C=38.9 Hz); HRMS m/z calculated for
[13C1C17H26O3] 291.1916, found 291.1923.
13C1-1-[3-(2-hydroxyethyl)-2,2-dimethylcyclobutyl]ethanone (9)
To a solution of methyl ketone 8 (300 mg, 1.03 mmol) in a mixture of
CH2Cl2:H2O (20:1, 5 ml: 0.25 ml) was added DDQ (281 mg, 1.24 mmol). The
reaction was stirred for 1 h, then filtered through Celite. The retentate was
washed with CH2Cl2 and the filtrates were combined and washed with water
and brine, dried (Na2SO4), and concentrated in vacuo. Purification of the
residue by column chromatography (SiO2; pet. ether:EtOAc, 8:2) provided
alcohol 9 as a colorless oil (160 mg, 91%); Rf=0.40 (pet. ether:EtOAc, 1:1); IR
3404, 2949, 2912, 2853, 1703 cmꢃ1; 1H NMR d 0.87 (s, 3H), 1.30 (s, 3H), 1.42–
1.51 (m, 1H), 1.58–1.66 (m, 1H), 1.83–2.08 (m, 3H), 2.04 (d, 3H,
J
C,H=126.8 Hz), 2.84 (dd, 1H, J=10.0, 7.2 Hz), 3.53–3.63 (m, 2H); 13C
2
NMR d 17.2, 23.0, 30.1, 30.4, 33.0, 38.6, 43.2, 54.3 (d, JC,C=12.9 Hz), 61.1,
208.1 (d, JC,C=39.5 Hz), HRMS calculated for [13C1C9H18O2] 171.1340,
1
found 171.1341.
13C1-(3-acetyl-2,2-dimethylcyclobutyl)acetaldehyde (13C1-1)
To a solution of alcohol 9 (135 mg, 0.788 mmol) in CH2Cl2 (5 ml) were added
PCC (255 mg, 1.18 mmol) and NaOAc (97 mg, 1.18 mmol). The reaction
mixture was stirred at rt 2 h whereupon Florisil1 was added to adsorb the
chromium salts. The reaction suspension was filtered through a short pad of
Celite1, and the retentate was washed with CH2Cl2. The organic filtrates were
combined and concentrated in vacuo. The residue was purified by column
chromatography (SiO2, pet ether:EtOAc, 8:2) to afford 13C1-1 (120 mg, 90%)
as a colorless oil; Rf=0.50 (pet ether:EtOAc, 1:1); IR 2956, 2905, 2847, 1720,
1
1703 cmꢃ1; H NMR d 0.85 (s, 3H), 1.34 (s, 3H), 1.90–2.05 (m, 2H), 2.05 (d,
3H, JC,H=127.2 Hz), 2.38–2.53 (m, 3H), 2.93 (dd, 1H, J=10.0, 7.6 Hz), 9.74
(t, 1H, J=1.6 Hz); 13C NMR d 17.6, 22.8, 30.1, 30.3, 35.7, 43.2, 45.1, 54.3 (d,
1
2JC,C=12.9 Hz), 201.4, 207.4 (d, JC,C=38.7 Hz); HRMS calculated for
[13C1C9H16O2] 169.1184, found 169.1185.
References
1. Van den Bergh V, Coeckelberghs H, Vankerckhoven H, Compernolle F, Vinckier
C. Anal Bioanal Chem 2004; 379: 484–494, and references therein.
Copyright # 2005 John Wiley & Sons, Ltd.
J Label Compd Radiopharm 2005; 48: 223–229