Stefan Gruber and Paul S. Pregosin
FULL PAPERS
Preliminary tests on acyclic 1,3-diketones, and a few 1,3-
diesters, were not successful under our very mild conditions,
in the absence of base.
(m, 1H), 5.121–4.93 (m, 3H), 2.36 (brs, 4H), 1.05 (s, 6H);
13C NMR (DMF-d7, 75 MHz): d=183.3, 143.6, 139.6, 130.3,
129.3, 127.7, 115.5, 114.6, 47.0, 43.1, 31.8, 27.7; HR-EI-MS:
m/z=290.1068, calcd. for [C17H19ClO2 ]: 290.1068.
3-Hydroxy-5,5-dimethyl-2-[1-(thiophen-2-yl)allyl]cyclo-
+
3-Hydroxy-5,5-dimethyl-2-(1-phenylallyl)cyclohex-2-
enone: Crystallized from EtOAc at À308C; yield: 78%;
1
hex-2-enone: Crystallized from Et2O at À308C; yield: 77%;
white solid; mp 129–1308C; H NMR (DMF-d7, 300 MHz):
1
white solid; mp 131–1328C; H NMR (DMF-d7, 300 MHz):
d=11.0 (brs, 1H) 7.47–7.28 (m, 5H), 6.83–6.71 (m, 1H),
5.28–5.14 (m, 3H), 2.54 (brs, 4H), 1.23 (s, 6H); 13C NMR
(DMF-d7, 75 MHz): d=184.0, 144.6, 140.4, 127.9, 127.7,
125.4, 116.2, 114.4, 47.2, 43.9, 32.0, 27.9; HR-EI-MS: m/z=
d=11.2 (brs, 1H), 7.42 (d, 1H, J=5 Hz), 7.09–7.07 (m, 1H),
6.96–6.94 (m, 1H), 6.96–6.94 (m, 1H), 6.80–6.68 (m, 1H),
5.31–5.17 (m, 3H), 2.53 (brs, 4H), 1.24 (s, 6H); 13C NMR
(DMF-d7, 75 MHz): d=82.6, 148.7, 140.0, 126.4, 123.3, 123.0,
116.0, 114.3, 47.0, 39.9, 31.8, 27.8; HR-EI-MS: m/z=
262.1022, calcd. for [C15H18O2S·+]: 262.1022.
+
256.1463, calcd. for [C17H20O2 ]: 256.1458.
2-[1-(o-Chlorophenyl)allyl]-3-hydroxy-5,5-dimethylcyclo-
hex-2-enone: Crystallized from EtOAc at À308C; yield:
75%; white solid; mp 169–1708C; 1H NMR (DMF-d7,
300 MHz): d=10.8 (brs, 1H), 7.56 (d, 1H, J=8 Hz), 7.36–
7.17 (m, 3H), 6.40–6.31 (m, 1H), 5.22 (d, 1H, J=7 Hz),
5.06–4.98 (m, 2H), 2.34 (brs, 4H), 1.05 (s, 6H); 13C NMR
(DMF-d7, 75 MHz): d=141.9, 139.1, 133.5, 131.3, 129.1,
2-Allyl-5,5-dimethyl-2-(1-phenylallyl)cyclohexane-1,3-
dione
3-Hydroxy-5,5-dimethyl-2-(1-phenylallyl)cyclohex-2-enone
(0.80 mmol) was added to a CH3CN solution (0.8 mL) of
À
127.4, 126.4, 114.5, 114.1, 47.3, 41.7, 31.8, 27.9, C O not ob-
(h3-C3H5)(p-
allyl alcohol (0.88 mmol) and [RuACHTUNTRGENNUG(Cp*)ACHTUNGTRENNUGN
served;
HR-EI-MS:
m/z=290.1057,
calcd.
for
MeC6H4SO3)2], (3) (0.025 g, 0.04 mmol). After addition of
CH2Cl2 (3.4 mL) the reaction mixture was refluxed for 16 h
at 708, then evaporated under vacuum and separated by
column chromatography on silica gel (hexane/EtOAc gradi-
ent from 8:1 to 6:1). The product was dried under vacuum
+
[C17H19ClO2 ]: 290.1068
3-Hydroxy-5,5-dimethyl-2-(1-(naphthalen-1-yl)allyl)cyclo-
hex-2-enone: Crystallized from EtOAc at À308C; yield:
70%; white solid; mp 165–1668C; 1H NMR (DMF-d7,
300 MHz): d=11.0 (brs, 1H), 8.37–7.58 (m, 7H), 6.81–6.70
(m, 1H), 5.82 (d, 1H, J=7 Hz), 5.32–5.26 (m, 2H), 2.56–
2.43 (m, 4H), 1.15 (s, 6H); 13C NMR (DMF-d7, 75 MHz):
d=140.2, 139.9, 133.9, 132.2, 128.6, 126.6, 126.2, 125.5, 125.2,
1
to afford a very viscous oil; yield: 140 mg (60%); H NMR
(CDCl3, 700 MHz): d=7.29 (t, 2H, J1 =8 Hz, J2 =7 Hz), 7.24
(t, 1H, J1 =8 Hz, J2 =7 Hz), 7.08 (d, 2H, J1 =8 Hz), 6.32 (dt,
1H, J1 =17 Hz, J2 =11 Hz), 5.58–5.54 (m, 1H), 5.21 (dd, 1H,
J1 =1 Hz, J1 =11 Hz), 5.13 (d, 1H, J=17 Hz), 5.07 (dd, 1H,
J1 =18 Hz, J2 =1 Hz), 5.00 (dd, 1H, J1 =11 Hz, J2 =1 Hz),
3.77 (d, 1H, J=11 Hz), 2.66 (dd, 1H, J1 =13 Hz, J1 =7 Hz),
2.58 (dd, 1H, J1 =13 Hz, J1 =7 Hz), 2.42 (dd, 1H, J1 =15 Hz,
J1 =2 Hz), 2.38–2.36 (m, 2H), 2.06 (d, 1H, J=15 Hz), 0.85
(s, 3H), 0.77 (s, 3H); 13C NMR (CDCl3 176 MHz): d=209.7,
209.3, 139.2, 135.5, 133.4, 129.2, 128.5, 127.5, 119.5, 118.5,
71.3, 57.8, 54.3, 54.0, 37.5, 30.4, 30.1, 28.1; HR-EI-MS: m/z=
À
125.1, 124.4, 115.8, 113.8, 47.1, 40.3, 31.7, 27.7, C O not ob-
served; HR-EI-MS: m/z=306.1618,calcd. for [C21H22O2 ]:
+
306.1614.
3-Hydroxy-5,5-dimethyl-2-(1-o-tolylallyl)cyclohex-2-
enone: Crystallized from EtOAc at À308C; yield: 77%;
1
white solid; mp 151–1528C; H NMR (DMF-d7, 300 MHz):
d=10.7 (brs, 1H), 7.46 (d, 1H, J=7 Hz), 7.12–7.04 (m, 3H),
6.51–6.39 (m, 1H), 5.05–4.91 (m, 3H), 2.35–2.32 (m, 7H),
1.04 (s, 6H); 13C NMR (DMF-d7, 75 MHz): d=142.6, 140.8,
136.2, 129.9, 129.2, 125.6, 125.4, 115.6, 112.9, 47.6, 41.5, 31.8,
+
296.1773, calcd. for [C20H24O2 ]: 296.1771.
À
27.9, 19.3, C O not observed; HR-EI-MS: m/z=270.1612,
calcd. for [C18H22O2 ]: 270.1614.
8,8-Dimethyl-1-phenylspiroACTHNUTRGNEUGN[4.5]dec-2-ene-6,10-dione
+
3-Hydroxy-2-[1-(p-methoxyphenyl)allyl]-5,5-dimethylcy-
clohex-2-enone: Crystallized from EtOAc at À308C; yield:
73%; white solid; mp 126–127; 1H NMR (DMF-d7,
300 MHz): d=10.8 (brs, 1H), 7.19 (d, 2H, J=8 Hz), 6.83 (d,
2H, J=8 Hz), 6.63–6.51 (m, 1H), 5.07–4.89 (m, 3H), 3.77 (s,
3H), 2.35 (brs, 4H), 1.05 (s, 6H); 13C NMR (DMF-d7,
75 MHz): d=157.6, 140.7, 136.3, 128.5, 116.2, 113.8, 113.2,
A mixture of 2-allyl-5,5-dimethyl-2-(1-phenylallyl)-cyclohex-
ane-1,3-dione (0.11 mmol) and Grubbꢁs catalyst [bis(tricylo-
hexylphosphine)benzylideneruthenium(IV)
dichloride]
(5 mg, 0.006 mmol) in dry CH2Cl2 (4 mL) was stirred at
room temperature for 14 h under N2 atmosphere. The reac-
tion mixture was evaporated under vacuum and separated
by column chromatography on silica gel (hexane/EtOAc=
6:1). The product was dried under vacuum to afford a white
À
54.8, 47.1, 43.1, 31.8, 27.8, C O not observed; HR-EI-MS:
+
1
m/z=286.1563, calcd. for [C18H22O3 ]: 286.1563.
solid; yield: 29 mg (96%); mp 135–1368C; H NMR (CDCl3,
3-Hydroxy-5,5-dimethyl-2-(1-(naphthalene-2-yl)allyl)cy-
clohex-2-enone: Crystallized from EtOAc at À308C; yield:
79%; white solid; mp 121–1238C; 1H NMR (DMF-d7,
300 MHz): d=10.9 (brs, 1H), 7.86–7.44 (m, 7H), 6.80–6.68
(m, 1H), 5.22–5.15 (m, 3H), 2.42 (brs, 4H), 1.10 (s, 6H);
13CNMR (DMF-d7, 75 MHz): d=143.0, 140.0, 133.6, 132.0,
127.6, 127.5, 127.2, 126.8, 125.8, 125.3, 125.1, 115.9, 114.6,
700 MHz): d=7.30–7.27 (m, 3H), 7.13 (d, 2H, J1 =7 Hz),
6.02–6.00 (m, 1H,), 5.38–5.36 (m, 1H), 4.14 (d, 1H, J=
1 Hz), 3.25 (dd, 1H, J1 =17 Hz, J1 =3 Hz), 3.05–3.01 (m,
2H), 2.51 (dd, 1H, J1 =15 Hz, J1 =3 Hz), 2.02 (dd, 1H, J1 =
15 Hz, J1 =3 Hz), 1.74 (d, 1H, J=15 Hz), 1.04 (s, 3H), 0.76
(s, 3H); 13C NMR (CDCl3 176 MHz): d=207.0, 206.1, 138.8,
131.6, 129.2, 128.6, 128.4, 128.0, 75.8, 63.1, 53.8, 51.6, 34.0,
30.6, 30.1, 26.7; HR-EI-MS: m/z=268.1456, calcd. for
À
47.0, 43.9, 31.8, 27.8, C O not observed; HR-EI-MS: m/z=
+
+
[C18H20O2 ]: 268.1458.
306.1613, calcd. for [C21H22O2 ]: 306.1614.
2-[1-(p-chlorophenyl)allyl]-3-hydroxy-5,5-dimethylcyclo-
hex-2-enone: Crystallized from Et2O/hexane at À308C;
1
yield: 62%; white solid; mp 135–1378C; H NMR (DMF-d7,
300 MHz): d=10.9 (brs, 1H), 7.33–7.26 (m, 4H), 6.56–6.47
3240
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 3235 – 3242