DEDICATED CLUSTER
FULL PAPERS
Henrik SundØn et al.
7-(4-Methoxyphenyl)-5,5-dimethyl-8-nitrobicyclo-
1H), 2.70–2.67 (m, 1H), 2.54–2.50 (m, 2H), 2.30, 2.20 (m,
1H), 2.04–1.86 (m, 2H), 1.76–1.66 (m, 1H); 13C NMR
(100 MHz, CDCl3): d=211.8, 141.1, 129.2, 127.7, 126.8, 91.2,
47.5, 45.0, 42.3, 34.4, 23.4, 18.2; HR-MS (ESI): m/z=
268.0941, calcd. for [M+Na]+(C14H15NO3Na): 268.0944;
[a]2D5: À13.2 (c 1.0, CHCl3). The enantiomeric excess was de-
termined by HPLC on Daicel Chiralpak OD-H with i-
hexane/i-PrOH (95:5) as the eluent. Flow: 0.5 mLminÀ1; tR
minor isomer=64.9 min; major isomer=50.1 min.
ACHTREUNG
[3.2.2]nonan-6-one (3g): 1H NMR
8-Nitro-9-phenylbicycloACHTREUNG
(300 MHz, CDCl3): d=1.59 (m, 1H), 1.79–2.05 (m, 5H),
2.62 (d, J=8.7 Hz, 2H), 2.83 (t, J=4.5 Hz, 1H), 3.14 (m,
1H), 4.29 (d, J=7.3 Hz, 1H), 4.74 (dd, J=7.4, 4.2 Hz, 1H),
7.07 (d, 8.4, 2H), 7.22–7.31 (m, 3H); 13C NMR (75 MHz,
CDCl3): d=20.1, 26.6, 32.7, 35.0, 42.1, 46.5, 53.5, 92.4, 126.7,
127.5, 129.3, 143.5, 211.2; HR-MS (ESI): m/z=282.1104,
calcd. for [M+Na]+ (C15H17NNaO3): 282.1101; [a]2D5: À25.5
(c 1.0, CHCl3). The enantiomeric excess was determined by
HPLC with an AD column (i-hexane:i-PrOH=94:6, l=
210 nm, 0.5 mLminÀ1); tR minor enantiomer=24.8 min,
5,5-Dimethyl-8-nitro-7-(4-nitrophenyl)-bicyclo-
ACHTREUNG
[2.2.2]octan-2-one (3c): 1H NMR (400 MHz, CDCl3): d=
8.18 (d, J=8.8 Hz, 2H), 7.37 (d, J=8.8 Hz, 2H), 4.54–4.50
(m, 1H), 4.34–4.31 (m, 1H), 3.03–3.00 (m, 1H), 2.94–2.85
(m, 1H), 2.63–2.60 (m, 1H), 2.40–2.34 (m, 1H), 2.06–2.00
(m, 1H), 1.81–1.75 (m, 1H), 1.16 (s, 3H), 1.13 (s, 3H);
13C NMR (100 MHz, CDCl3): d=211.0, 148.2, 147.4, 128.3,
124.2, 89.3, 50.4, 44.0, 43.1, 40.8, 39.9, 30.7, 30.6, 29.5. 126.8,
91.2, 47.5, 45.0, 42.3, 34.4, 23.4, 18.2; HR-MS (ESI): m/z=
319.1293, calcd. for [M+Na]+ (C16H19N2O5): 319.1288; [a]D25:
À3.6 (c 1.0, CHCl3). The enantiomeric excess was deter-
mined by HPLC on Daicel Chiralpak OD-H with i-hexane/
i-PrOH (95:5) as the eluent, flow: 1.0 mLminÀ1; tR minor
isomer=72.4 min, major isomer=67.1 min.
major enantiomer=31.2 min.
1
6-Nitro-5-phenylbicyclo[2.2.1]heptan-2-one (3h): H NMR
A
(400 MHz, CDCl3): d=7.42–7.18 (m, 5H), 5.16–5.11 (m,
1H), 3.95–3.90 (m, 1H), 3.48–3.44 (m, 1H), 2.99 (s, 1H),
2.30–2.22 (m, 2H), 2.06–1.96 (m, 2H); 13C NMR (100 MHz,
CDCl3): d=211.6, 139.3, 129.3, 127.7, 126.7, 92.6, 55.5, 44.9,
41.8, 38.9, 35.4; HR-MS (ESI): m/z=254.0786, calcd. for
[M+Na]+ (C13H13NO3Na): 254.0788; [a]2D5: À2.4 (c 1.0,
CHCl3). The enantiomeric excess was determined by HPLC
on Daicel Chiralpak OD-H with i-hexane/i-PrOH (95:5) as
the eluent, flow: 0.5 mLminÀ1; tR minor isomer=52.2 min;
major isomer=65.6 min.
5,5-Dimethyl-7-(naphthalen-2-yl)-8-nitrobicyclo-
ACHTREUNG
[2.2.2]octan-2-one (3d): 1H NMR (400 MHz, CDCl3): d=
1.16 (s, 6H), 1.79 (dd, J=14.3, 2.7 Hz, 1H), 2.07 (dd, J=
13.9, 3.1 Hz, 1H), 2.44 (d, J=2.5 Hz, 1H), 2.72 (q, J=
2.6 Hz, 1H), 2.90 (dd, J=20.0, 2.9 Hz, 1H), 3.02 (q, J=
2.7 Hz, 1H), 4.40 (dd, J=8.0, 1.6 Hz, 1H), 4.70 (dq, 1.0,
0.7 Hz, 1H), 7.27 (m, 2H), 7.47 (m, 2H), 7.65 (d, J=1.8,
1H) , 7.80 (m, 3H); 13C NMR (100 MHz, CDCl3): d=29.5,
30.7, 30.9, 40.4, 41.0, 43.3, 44.4, 51.1, 90.0, 125.0, 126.1, 126.3,
126.5, 127.6, 129.1, 129.1, 132.6, 133.4, 138.5, 211.9; HR-MS
(ESI): m/z=346.1425, calcd. for [M+Na]+ (C20H21NNaO3):
346.1414; [a]2D5: À59.7 (c 1.0, CHCl3). The enantiomeric
excess was determined by HPLC with an AD column (i-
hexane:i-PrOH=95:5, l=254 nm, 0.5 mLminÀ1): tR major
enantiomer=20.7 min, minor enantiomer=24.6 min.
7-(4-Bromophenyl)-5,5-dimethyl-8-nitrobicyclo-
1
A
(s, 3H), 1.13 (s, 3H), 1.74 (dd, J=14.3, 2.7 Hz, 1H),1.99 (dd,
J=14.3, 3.5 Hz, 1H), 2.32 (dd, J=19.9, 3.0 Hz, 1H), 2.85
(dd, J=19.8, 3.2 Hz, 1H), 2.96 (q, J=2.8 Hz, 1H), 4.18 (dd,
J=8.1, 1.5 Hz, 1H), 4.49 (ddd, 8.1, 2.1, 1.0 Hz, 1H), 7.05 (d,
J=8.4 Hz, 2H), 7.43 (d, J=8.4 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=29.4, 30.6, 30.8, 40.1, 41.0, 42.7, 44.2,
51.0, 89.9, 121.7, 128.9, 132.2, 140.2, 211.6; HR-MS (ESI): m/
z=374.0373, calcd. for [M+Na]+ (C16H19NBrNaO3):
374.0362; [a]2D5: À57.3 (c 1.0, CHCl3). The enantiomeric
excess was determined by HPLC with an AD column (i-hex-
ane:i-PrOH=98:2, l=254 nm, 1 mLminÀ1); tR major enan-
tiomer=28.5 min, minor enantiomer=47.3 min.
7-Furan-2-yl-5,5-dimethyl-8-nitrobicycloACHTRE[UNG 2.2.2]octan-2-one
1
(3e): H NMR (300 MHz, CDCl3): d=1.05 (s, 3H), 1.10 (s,
3H), 1.74 (dd, J=14.3, 2.9 Hz, 1H), 1.94 (dd, J=14.3,
3.3 Hz, 1H), 2.29 (dd, J=19.5, 2.7 Hz, 1H), 2.68 (q, J=
2.7 Hz, 1H), 2.77 (dd, J=19.6, 3.4 Hz, 1H), 3.0 (q, J=
2.8 Hz, 1H), 4.34 (dd, J=7.2, 1.9 Hz, 1H), 4.67 (ddd, 7.2,
2.2, 0.7 Hz, 1H), 6.16 (d, 3.3, 1H), 6.27 (dd, J=3.3, 1.9 Hz,
1H), 7.29 (dd, J=1.8, 0.7 Hz, 1H); 13C NMR (75 MHz,
CDCl3): d=29.3, 30.4, 30.8, 37.0, 40.4, 44.2, 49.0, 87.0, 106.5,
110.4, 142.6, 153.1, 210.6; HR-MS (ESI): m/z=286.1061,
calcd. for [M+Na]+ (C14H17NNaO4): 286.1050; [a]2D5: À14.5
(c 1.0, CHCl3). The enantiomeric excess was determined by
HPLC with an AD column (i-hexane:i-PrOH=95:5, l=
254 nm, 0.5 mLminÀ1): tR major enantiomer=24.3 min,
minor enantiomer=31.7 min.
6-(2-Bromophenyl)-8,8-dimethyl-5-nitrobicyclo-
AHCTREUNG
[2.2.2]octan-2-one (3k): 1H NMR (300 MHz, CDCl3): d=
1.16 (s, 3H), 1.25 (s, 3H), 1.72 (dd, J=14.4, 2.4 Hz, 1H),
2.07 (dd, J=14.4, 3.6 Hz, 1H), 2.37 (dd, J=19.6, 2.8 Hz,
1H), 2.43 (q, J=1.6 Hz, 1H), 2.85 (dd, J=19.6, 2.8 Hz, 1H),
3.06 (q, J=2.4 Hz, 1H), 4.75 (d, J=8.0 Hz, 1H), 4.85 (dd,
J=8.0, 1.6 Hz, 1H), 6.84 (d, J=7.8 Hz, 1H), 7.12 (t, J=
8.0 Hz, 1H), 7.24–7.27 (m, 1H), 7.63 (d J=8.0 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=29.6, 30.6, 30.8, 39.4, 40.6,
42.0, 44.0, 50.9, 87.2, 125.3, 126.4, 128.0, 129.1, 133.8, 138.9,
210.6; HR-MS (ESI): m/z=374.0366, calcd. for [M+Na]+
(C16H18BrNNaO3): 374.0362; [a]2D5: À44.2 (c 1.0, CHCl3). The
enantiomeric excess was determined by HPLC with an AD
column (i-hexane:i-PrOH=93:7, l=230 nm, 1 mLminÀ1); tR
minor enantiomer=11.2 min, major enantiomer=15.9 min.
[2.2.2]octan-2-one (3f): 1H NMR
5-Nitro-6-phenylbicycloACHTREUNG
(400 MHz, CDCl3): d=7.35–7.20 (m, 3H), 7.10–7.05 (m,
2H), 4.84–4.80 (m, 1H), 4.17–4.13 (m, 1H), 2.98–2.92 (m,
2554
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2007, 349, 2549 – 2555