Seda Ünaldi et al.
FULL PAPERS
1H, CHO); 13C NMR (75 MHz, CDCl3): d¼12.3 (CH3), 20.4
(CH2), 21.4 (CH2), 23.3 (CH2), 28.6 (CH2), 30.0 (CH2), 32.1
(CH2), 33.1 (CH2), 46.5 (Cq), 60.9 (Cq), 79.8 (CH), 83.8 (CH),
110.9/124.2/125.2/126.3/127.2/128.0/130.7 (CH and Cq of aryl
ane:i-PrOH¼200:1, 78% ee, major enantiomer appears at
higher retention time.
rac-11a was obtained from 10a (130 mg, 0.25 mmol) as a col-
1
ourless oil; yield: 94 mg (72%); H NMR (300 MHz, CDCl3):
¼
carbons), 206.1 (C O); IR (film): n¼2958, 2916, 2860 (Caliph
-
d¼0.93 (t, 3H, CH3), 1.16–1.86 (m, 14H, CH2), 3.54 (d, 1H,
J¼11.7 Hz, CH), 3.69 (d, J¼11.6 Hz, 1H, CH), 4.54 (s, 1H,
CH), 4.58 (s, 1H, CH), 7.12–7.40 (m, 8H, CH); 13C NMR
(75 MHz, CDCl3): d¼13.0 (CH3), 20.4 (CH2), 21.8 (CH2),
23.7 (CH2), 28.5 (CH2), 30.3 (CH2), 32.7 (CH2), 33.9 (CH2),
46.8 (Cq), 49.4 (Cq), 63.9 (CH2), 79.6 (CH), 83.8 (CH), 111.5/
124.4/125.8/126.6/127.3/128.2/130.4/130.5 (CH and Cq of aryl
carbons); IR (film): n¼3370 (OH), 2958, 2930, 2867 cmꢀ1
(Caliph-H).
(1R,6S,7R,9S)-{9-(4-Bromophenyl)-6-butyl-7-phenyl-8-ox-
abicyclo[4.3.0]non-1-yl}methanol (11b): According to GP2,
11b was obtained from 10b (110 mg, 0.25 mmol) as a colourless
oil; yield: 80 mg (72%); RF ¼0.18 (petroleum ether:Et2O¼
4:1); [a]2D0: þ30.1 (c 0.48, CHCl3). Chiral HPLC: chiragrom-
2, hexane:i-PrOH¼200:1, 81% ee, major enantiomer appears
at higher retention time.
H), 1721 cmꢀ1 (C O).
¼
(1S,6S,7R,9S)-7-(4-Bromophenyl)-6-methyl-9-[(E)-prop-1-
enyl]-8-oxabicyclo[4.3.0]nonane-1-carboxaldehyde (10c): Ac-
cording to GP1, 10c was obtained from allyl carbamate 7c
(123 mg, 0.28 mmol) and (E)-2-butenal (28 mg, 0.40 mmol)
as a colourless oil; yield: 63 mg (62%); RF ¼0.70 (petroleum
ether:Et2O¼4:1); [a]D20: ꢀ94.2 (c 0.50, CHCl3). Chiral
HPLC: chiragrom-1, hexane:i-PrOH¼200:1, 91% ee, major
enantiomer appears at higher retention time.
rac-10c was obtained from allyl carbamate 7c (123 mg,
0.28 mmol) and (E)-2-butenal (28 mg, 0.40 mmol) as a colour-
less oil; yield: 66 mg (65%); 1H NMR (300 MHz, CDCl3): d¼
1.18 (s, 3H, CH3), 1.33–2.16 (m, 11H, CH2 and CH3), 4.45 (d,
1H, CH), 4.97 (s, 1H, CH), 5.55 (m, 1H, CH), 5.81 (m, 1H,
CH), 7.18 (m, 2H, CH), 7.39 (m, 2H, CH), 9.64 (s, 1H, CHO);
13C NMR (75 MHz, CDCl3): d¼17.8 (CH3), 19.8 (CH3), 21.2
(CH2), 21.4 (CH2), 26.8 (CH2), 36.1 (CH2), 47.7 (Cq), 61.2
(Cq), 85.2 (CH), 86.8 (CH), 121.6 (Cq), 127.3 (CH), 127.8
rac-11b was obtained from 10b (110 mg, 0.25 mmol) as a col-
1
ourless oil; yield: 77 mg (70%); H NMR (300 MHz, CDCl3):
d¼0.93 (t, 3H, CH3), 1.14–1.86 (m, 14H, CH2), 3.58 (d, 1H,
J¼11.7 Hz, CH), 3.71 (d, J¼11.8 Hz, 1H, CH), 4.84 (s, 1H,
CH), 4.99 (s, 1H, CH), 7.11–7.28 (m, 9H, CH); 13C NMR
(75 MHz, CDCl3): d¼12.7 (CH3), 21.2 (CH2), 21.9 (CH2),
23.8 (CH2), 26.2 (CH2), 29.6 (CH2), 31.7 (CH2), 33.5 (CH2),
45.4 (Cq), 49.9 (Cq), 64.6 (CH2), 79.9 (CH), 83.6 (CH), 111.9/
124.4/125.7/126.3/127.2/127.6/128.9/130.5 (CH and Cq of aryl
carbons); IR (film): n¼3426 (OH), 2979, 2923, 2853 cmꢀ1
(Caliph-H).
(1R,6S,7R,9S)-{7-(4-Bromophenyl)-6-methyl-9-[(E)-prop-
1-enyl]-8-oxabicyclo[4.3.0]non-1-yl}methanol (11c): Accord-
ing to GP2, 11c was obtained from 10c (61 mg, 0.17 mmol) as
a colourless oil; yield: 45 mg (73%); RF ¼0.16 (petroleum
ether:Et2O¼4:1); [a]D20: ꢀ80.0 (c 0.25, CHCl3). Chiral
HPLC: chiragrom-1, hexane:i-PrOH¼200:1, 91% ee, major
enantiomer appears at higher retention time.
¼
(CH), 131.3 (CH), 132.2 (CH), 138.4 (Cq), 203.3 (C O); IR
(film): n¼2958, 2920, 2853 (Caliph-H), 1719 cmꢀ1 (C O).
¼
(1S,2S,4R,5S)-4-(4-Bromophenyl)-5-methyl-2-(1-methyl-
ethyl)-3-oxabicyclo[3.3.0]octane-1-carboxaldehyde (10d): Ac-
cording to GP1, 10d was obtained from allyl carbamate 7d
(106 mg, 0.25 mmol) and 2-methylpropanal (29 mg,
0.40 mmol) as a colourless oil; yield: 55 mg (63%); RF ¼0.71
(petroleum ether:Et2O¼4:1); [a]2D0: ꢀ119.1 (c 0.51, CHCl3).
Chiral HPLC: chiragrom-2, hexane:i-PrOH¼200:1, 96% ee,
major enantiomer appears at lower retention time.
rac-10d was obtained from allyl carbamate rac-7d (106 mg,
0.25 mmol) and 2-methylpropanal (29 mg, 0.40 mmol) as a col-
1
ourless oil; yield: 54 mg (61%); H NMR (300 MHz, CDCl3):
d¼0.95 (s, 3H, CH3), 1.02 (d, 6H, CH3), 1.35–2.19 (m, 6H,
CH2), 2.15 (m, 1H, CH), 4.14 (d, J¼6.5 Hz, 1H, CH), 4.43 (s,
1H, CH), 7.14 (m, 2H, CH), 7.34 (m, 2H, CH), 9.59 (s, 1H,
CHO); 13C NMR (75 MHz, CDCl3): d¼17.8 (CH3), 19.5
(CH3), 19.6 (CH3), 21.2 (CH2), 21.5 (CH2), 23.6 (CH2), 27.3
(CH), 47.7 (Cq), 61.5 (Cq), 75.5 (CH), 86.3 (CH), 121.4 (Cq),
rac-11c was obtained from 10c (61 mg, 0.17 mmol) as a col-
1
ourless oil; yield: 45 mg (74%); H NMR (300 MHz, CDCl3):
d¼0.40 (s, 3H, CH3), 1.16–2.26 (m, 11H, CH2 and CH3), 3.56
(d, 1H, J¼11.7 Hz, CH), 3.73 (d, J¼11.7 Hz, 1H, CH), 4.06
(m, 1H, CH), 4.55 (s, 1H, CH), 5.77 (m, 2H, CH), 7.11 (m,
2H, CH), 7.38 (m, 2H, CH); 13C NMR (75 MHz, CDCl3): d¼
17.8 (CH3), 19.8 (CH3), 21.8 (CH2), 21.9 (CH2), 30.5 (CH2),
32.1 (CH2), 45.6 (Cq), 50.5 (Cq), 64.3 (CH2), 83.0 (CH), 88.5
(CH), 120.8 (Cq), 128.2/128.4/129.9/130.7/131.3/131.5 (CH
and Cq), 138.0 (Cq); IR (film): n¼3372 (OH), 2956, 2932,
2869 cmꢀ1 (Caliph-H).
(1R,2S,4R,5S)-{4-(4-Bromophenyl)-5-methyl-2-(1-methyl-
ethyl)-3-oxabicyclo[3.3.0]oct-1-yl}methanol (11d): According
to GP2, 11d was obtained from 10d (50 mg, 0.14 mmol) as a col-
ourless oil; yield: 37 mg (74%); RF ¼0.16 (petroleum ether:
Et2O¼4:1); [a]2D0: ꢀ42.7 (c 0.55, CHCl3). Chiral HPLC: chira-
grom-2, hexane:i-PrOH¼200:1, 96% ee, major enantiomer
appears at lower retention time.
¼
131.4 (CH), 132.5 (CH), 138.9 (Cq), 203.5 (C O); IR (film):
n¼2958, 2951, 2853 (Caliph-H), 1721 cmꢀ1 (C O).
¼
General Procedure for Synthesis of Alcohols 11 (GP2)
To a solution of aldehyde 10 (0.25 mmol) in Et2O(5 mL),
LiAlH4 (1 M solution in Et2O; 0.25 mmol) was added in small
portions at 08C. After stirring at 08C for 30 min and subse-
quently, at room temperature for 3 h, Et2O(20 mL) and a satu-
rated aqueous solution of NH4Cl (10 mL) were added. The
aqueous phase was extracted (Et2O , 2Â20 mL), the combined
solutions were dried over anhydrous MgSO4 and concentrated
under vacuum. The residue was purified by silica gel flash col-
umn chromatography (petroleum ether:Et2O¼4:1).
rac-11d was obtained from 10d (50 mg, 0.14 mmol) as a col-
1
ourless oil; yield: 38 mg (75%); H NMR (300 MHz, CDCl3):
(1R,6S,7R,9S)-{7,9-Di(4-bromophenyl)-6-butyl-8-oxabicy-
clo[4.3.0]non-1-yl}-methanol (11a): According to GP2, 11a was
obtained from 10a (130 mg, 0.25 mmol) as a colourless oil;
yield: 91 mg (70%); RF ¼0.18 (petroleum ether:Et2O¼4:1);
[a]2D0: ꢀ36.5 (c 0.65, CHCl3). Chiral HPLC: chiragrom-2, hex-
d¼0.43 (s, 3H, CH3), 1.04 (d, 6H, CH3), 1.33–2.16 (m, 6H,
CH2), 2.10 (m, 1H, CH), 3.53 (d, J¼11.7 Hz, 1H, CH), 3.75
(d, J¼1.7 Hz, 1H, CH), 4.13 (d, 1H, CH), 4.46 (s, 1H, CH),
7.13–7.42 (m, 4H, CH); 13C NMR (75 MHz, CDCl3); d¼17.4
1624
asc.wiley-vch.de
ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2005, 347, 1621 – 1626