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Experimental Procedures and Characterization of the Prepared Compounds
The 1H-NMR and 13C-NMR spectra were recorded in CDCl3 (internal standard: 7.26
ppm, 1H; 77.36 ppm, 13C) at room temperature using Varian 300 or 400 MHz
spectrometers. Mass data (ESI) were obtained with a Bruker MicrOTOF spectrometer.
Palladium pincer-complex 4 was prepared according to the procedure published by
Yao and co-workers.[1] The aldehydes (2) and allylic alcohols (1) were purchased
from Aldrich or prepared according to literature procedures.[2] Diboronic acid 3 was
purchased from Boron Molecular Ltd and were used as received. For column
chromatography, Merck silica gel 60 (230-400 mesh) was used.
General Procedure. The corresponding allyl alcohol 1 (0.15 mmol) was dissolved in
the DMSO/MeOH mixture (0.3/0.3 ml) followed by addition of tetrahydroxydiboron
3 (0.18 mmol), pincer complex 4 (0.0075 mmol, 5 mol %), p-toluene sulfonic acid 5
(0.0075 mmol, 5 mol %) and aldehyde 2 (0.18 mmol). This reaction mixture was
stirred for the allotted temperatures and times listed in Tables 1-2 and thereafter
quenched with water and extracted with diethyl ether. After evaporation of the ether
phase, the product 6 was purified by silica gel column chromatography. The reactions
do not require use of inert atmosphere or application of carefully dried solvents.
1,2-Diphenyl-3-buten-1-ol (6a). This compound was prepared according to the
above general procedure from 1a and 2a. The NMR data obtained for 6a are identical
with the literature[3] values. 1H NMR (CDCl3): 7.18 (m, 8H), 7.06 (m, 2H), 6.26 (ddd,
8.3 Hz, 10.3 Hz, 17.1 Hz, 1H), 5.28 (d, 10.3 Hz, 1H), 5.23 (d, 17.1 Hz, 1H), 4.86 (dd,
2.7 Hz, 8.3 Hz, 1H), 3.56 (t, 8.3 Hz, 1H), 2.31 (d, 2.7 Hz, 1H) 13C NMR (CDCl3):
142.2, 141.0, 138.2, 128.7, 128.7, 128.3, 127.8, 127.0, 126.9, 118.8, 77.6, 59.6.
HRMS (ESI): calc for [C16H16O - OH]+: m/z, 207.1168, found: 207.1168.
1-(4-Bromophenyl)-2-phenyl-3-buten-1-ol (6b). This compound was prepared
according to the above general procedure from 1a and 2b. The diastereoselectivity of
6b is assigned on the basis of 1H-NMR data given in the literature[4] for analog stereo
defined homoallyl alcohols. 1H NMR (CDCl3): 7.32 (d, 8.4 Hz, 2H), 7.21 (m, 3H),
7.04 (d, 7.7 Hz, 2H), 7.00 (d, 8.4 Hz, 2H), 6.22 (ddd, 8.5 Hz, 10.1 Hz, 17.1 Hz, 1H),
5.29 (d, 10.1 Hz, 1H), 5.24 (d, 17.1 Hz, 1H), 4.79 (d, 8.5 Hz, 1H), 3.48 (t, 8.5 Hz,
Eur. J. Org. Chem. 2006 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006 · ISSN 1434–193X
SUPPORTING INFORMATION
Title: Highly Selective and Robust Palladium-Catalyzed Carbon–Carbon Coupling between Allyl Alcohols and Aldehydes via Transient Allylboronic Acids Author(s): Nicklas Selander, Sara Sebelius, Cesar Estay, Kálmán J. Szabó* Ref. No.: O200600530
3
1H), 2.37 (bs, 1H). 13C NMR (CDCl3): 141.1, 140.5, 137.8, 131.3, 128.8, 128.7,
128.6, 127.1, 121.6, 119.2, 76.9, 59.7. HRMS (ESI): calc for [C16H15BrO - OH]+: m/z,
285.0273, found: 285.0268.
1-(4-Cyanophenyl)-2-phenyl-3-buten-1-ol (6c). This compound was prepared
according to the above general procedure from 1a and 2c. The NMR data obtained for
6c are identical with the literature[5] values. 1H NMR (CDCl3): 7.48 (d, 8.1 Hz, 2H),
7.22 (m, 5H), 7.02 (d, 8.1 Hz, 2H), 6.22 (ddd, 8.5 Hz, 10.2 Hz, 17.1 Hz, 1H), 5.31 (d,
10.2 Hz, 1H), 5.25 (d, 17.1 Hz, 1H), 4.87 (d, 8.5 Hz, 1H), 3.45 (t, 8.5 Hz, 1H), 2.47
(bs, 1H). 13C NMR (CDCl3): 147.5, 139.9, 137.2, 132.0, 129.0, 128.5, 127.7, 127.4,
119.7, 119.2, 111.5, 76.9, 59.8. HRMS (ESI): calc for [C17H15NO + H]+: m/z,
250.1226, found: 250.1227.
1-(4-Nitrophenyl)-2-phenyl-3-buten-1-ol (6d). This compound was prepared
according to the above general procedure from 1a and 2d. The NMR data obtained for
6d are identical with the literature[6] values. 1H NMR (CDCl3): 8.07 (d, 8.8 Hz, 2H),
7.27 (d, 8.8 Hz, 2H), 7.21 (m, 3H), 7.04 (m, 2H), 6.23 (ddd, 8.5 Hz, 10.3 Hz, 17.1 Hz,
1H), 5.31 (d, 10.3 Hz, 1H), 5.20 (d, 17.1 Hz, 1H), 4.92 (d, 8.5 Hz, 1H), 3.47 (t, 8.5
Hz, 1H), 2.54 (bs, 1H) 13C NMR (CDCl3): 149.5, 147.5, 139.9, 137.1, 129.0, 128.5,
127.8, 127.5, 123.4, 119.8, 76.7, 59.8. HRMS (ESI): calc for [C16H15NO3 + H]+: m/z,
270.1125, found: 270.1124.
1-(4-Acetylphenyl)-2-phenyl-3-buten-1-ol (6e). This compound was prepared
according to the above general procedure from 1a and 2e. The diastereoselectivity of
6e is assigned on the basis of 1H-NMR data given in the literature[4] for analog stereo
defined homoallyl alcohols. 1H NMR (CDCl3): 7.79 (d, 8.4 Hz, 2H), 7.22 (d, 8.4 Hz,
2H), 7.19 (t, 6.6 Hz, 2H), 7.16 (t, 6.6 Hz, 1H), 7.05 (d, 6.6 Hz, 2H), 6.24 (ddd, 8.2 Hz,
10.2 Hz, 17.1 Hz, 1H), 5.28 (d, 10.2 Hz, 1H), 5.23 (d, 17.1 Hz, 1H), 4.90 (d, 8.2 Hz,
1H), 3.52 (t, 8.2 Hz, 1H), 2.54 (s, 3H), 2.50 (bs, 1H). 13C NMR (CDCl3): 198.2,
147.6, 140.4, 137.6, 136.5, 128.9, 128.6, 128.3, 127.2, 127.2, 119.3, 77.1, 59.6, 26.9.
HRMS (ESI): calc for [C18H18O2+H]+: m/z, 267.1380, found: 267.1387.
3-Phenyl-1-nonen-4-ol (6f). This compound was prepared according to the above
general procedure from 1a and 2f, except that 0.20 mmol of aldehyde 2f was used in a
4
0.2/0.2 ml DMSO/MeOH mixture. The NMR data obtained for 6f are identical with
the literature[3b] values. 1H NMR (CDCl3): 7.28 (m, 5H), 6.13 (ddd, 8.8 Hz, 10.2 Hz,
16.9 Hz, 1H), 5.24 (d, 10.2 Hz, 1H), 5.20 (d, 16.9 Hz, 1H), 3.80 (tt, 3.6 Hz, 7.1 Hz,
1H), 3.25 (dd, 7.1 Hz, 8.8 Hz, 1H), 1.79 (d, 3.6 Hz, 1H), 1.30 (m, 8H), 0.85 (t, 7.1 Hz,
3H). 13C NMR (CDCl3): 142.1, 138.7, 129.0, 128.3, 127.0, 118.2, 74.3, 57.8, 34.7,
32.1, 25.7, 22.9, 14.4. HRMS (ESI): calc for [C15H22O - OH]+: m/z, 201.1638, found:
201.1638.
2-Pentyl-1-phenyl-3-buten-1-ol (6g). This compound was prepared according to
the above general procedure from 1b and 2a, except that a 0.2/0.2 ml DMSO/MeOH
mixture was used. The NMR data obtained for 6g are identical with the literature[7]
values. 1H NMR (CDCl3): 7.30 (m, 5H), 5.66 (ddd, 8.1 Hz, 10.2 Hz, 17.2 Hz, 1H),
5.25 (d, 10.2 Hz, 1H), 5.18 (d, 17.2 Hz, 1H), 4.39 (d, 8.1 Hz, 1H), 2.29 (p, 8.1 Hz,
1H), 2.19 (bs, 1H), 1.18 (m, 8H), 0.82 (t, 7.0, 3H). 13C NMR (CDCl3): 142.9, 139.8,
128.6, 127.9, 127.3, 119.0, 77.0, 53.1, 32.0, 30.7, 27.2, 22.8, 14.3. HRMS (ESI): calc
for [C15H22O - OH]+: m/z, 201.1638, found: 201.1634.
3-Pentyl-1-nonen-4-ol (6h). This compound was prepared according to the above
general procedure from 1b and 2f, except that 0.20 mmol of aldehyde 2f was used in a
0.2/0.2 ml DMSO/MeOH mixture. The diastereoselectivity of 6h is assigned on the
basis of 1H-NMR data given in the literature[7] for analog stereo defined homoallyl
alcohols. 1H NMR (CDCl3): 5.63 (ddd, 9.3 Hz, 10.3 Hz, 17.1 Hz, 1H), 5.17 (d, 10.3
Hz, 1H), 5.08 (d, 17.1 Hz, 1H), 3.44 (m, 1H), 1.99 (tt, 4.7 Hz, 9.3 Hz, 1H), 1.37 (m,
17H), 0.88 (m, 6H). 13C NMR (CDCl3): 139.4, 118.0, 74.0, 50.7, 35.0, 32.3, 32.2,
31.1, 27.4, 25.8, 23.0, 22.9, 14.4, 14.4. HRMS (ESI): calc for [C14H28O]+: m/z,
212.2135, found: 212.2138.
2-[(Benzyloxy)methyl]-1-phenyl-3-buten-1-ol (6i). This compound was prepared
according to the above general procedure from 1c and 2a. The NMR data obtained for
6i are identical with the literature[8] values. 1H NMR (CDCl3): 7.34 (m, 10H), 5.89
(ddd, 8.4 Hz, 10.4 Hz, 17.2 Hz, 1H), 5.20 (d, 10.4 Hz, 1H), 5.11 (d, 17.2 Hz, 1H),
4.92 (dd, 3.8 Hz, 5.0 Hz, 1H), 4.51 (s, 2H), 3.57 (dd, 5.9 Hz, 9.2 Hz, 1H), 3.52 (dd,
5.0 Hz, 9.2 Hz, 1H), 3.00 (d, 3.8 Hz, 1H), 2.71 (ddt, 5.0 Hz, 5.9 Hz, 8.4 Hz, 1H). 13C
NMR (CDCl3): 142.6, 138.2, 135.6, 128.7, 128.3, 128.0, 128.0, 127.6, 126.7, 118.8,
5
74.9, 73.7, 71.9, 51.7. HRMS (ESI): calc for [C18H20O2 + H]+: m/z, 269.1536, found:
259.1535.
1-Phenyl-2-vinyl-3-buten-1-ol (6j). This compound was prepared according to the
above general procedure from 1d and 2a. The NMR data obtained for 6j are identical
with the literature[9] values. 1H NMR (CDCl3): 7.31 (m, 5H), 5.86 (ddd, 7.2 Hz, 10.4
Hz, 17.1 Hz, 1H), 5.69 (ddd, 7.2 Hz, 10.6 Hz, 17.3 Hz, 1H), 5.24 (d, 10.4 Hz, 1H),
5.18 (d, 17.1 Hz, 1H), 5.05 (d, 10.6 Hz, 1H), 5.02 (d, 17.3 Hz, 1H), 4.60 (dd, 3.1 Hz,
7.2 Hz, 1H), 3.11 (q, 7.2 Hz, 1H), 2.19 (d, 3.1 Hz, 1H). 13C NMR (CDCl3): 142.1,
137.1, 137.1, 128.5, 128.0, 127.2, 118.7, 117.4, 76.5, 56.5. HRMS (ESI): calc for
[C12H14O - OH]+: m/z, 157.1012, found: 157.1015.
Ethyl 2-(2-hydroxy-2-phenylethyl)acrylate (6k). This compound was prepared
according to the above general procedure from 1e and 2a. The NMR data obtained for
6k are identical with the literature[10] values. 1H NMR (CDCl3): 7.37 (d, 7.8 Hz, 2H),
7.34 (t, 7.8 Hz, 2H), 7.26 (t, 7.8 Hz, 1H), 6.24 (s, 1H), 5.60 (s, 1H), 4.89 (dt, 3.8 Hz,
8.6 Hz, 1H), 4.23 (q, 7.2 Hz, 2H), 2.80 (dd, 3.8 Hz, 14.0 Hz, 1H), 2.69 (d, 3.8 Hz,
1H), 2.67 (dd, 8.6 Hz, 14.0 Hz, 1H), 1.32 (t, 7.2 Hz, 3H). 13C NMR (CDCl3): 168.1,
144.3, 137.5, 128.7, 128.5, 127.8, 126.1, 73.5, 61.4, 42.9, 14.5. HRMS (ESI): calc for
[C13H16O3 + H]+: m/z, 221.1172, found: 221.1170.
4-Phenyl-2-methylenebutyrolactone (6l). This compound was prepared according
to the above general procedure from 1e and 2a, except that 50 mol% p-
toluenesulfonic acid was used. The NMR data obtained for 6l are identical with the
literature[11] values. 1H NMR (CDCl3): 7.36 (m, 5H), 6.31 (t, 2.6 Hz, 1H), 5.69 (t, 2.6
Hz, 1H), 5.53 (dd, 6.7 Hz, 7.8 Hz, 1H), 3.41 (ddt, 2.6 Hz, 7.8 Hz, 17.1 Hz, 1H), 2.92
(ddt, 2.6 Hz, 6.7 Hz, 17.1 Hz, 1H). 13C NMR (CDCl3): 170.5, 140.2, 134.6, 129.2,
128.9, 125.7, 122.8, 78.3, 36.6. HRMS (ESI): calc for [C11H10O2 + H]+: m/z,
175.0754, found: 175.0755.
2-Cyclohexenyl(phenyl)methanol (6m). This compound was prepared according
to the above general procedure from 1f and 2a. The NMR data obtained for 6m are
identical with the literature[9] values. 1H NMR (CDCl3): 7.35 (d, 4.4 Hz, 4H), 7.28
(m, 1H), 5.82 (dt, 4.9 Hz, 10.2 Hz, 1H), 5.39 (dd, 5.1 Hz, 10.2 Hz, 1H), 4.59 (dd, 2.8
6
Hz, 6.5 Hz, 1H), 2.51 (ddt, 5.1 Hz, 6.5 Hz, 17.4 Hz, 1H), 1.99 (m, 2H), 1.87 (d, 2.8
Hz, 1H), 1.74 (m, 2H), 1.53 (m, 2H). 13C NMR (CDCl3): 143.2, 130.8, 128.6, 128.4,
127.8, 126.9, 77.7, 43.4, 25.6, 24.2, 21.5. HRMS (ESI): calc for [C13H16O + H]+: m/z,
189.1274, found: 189.1273.
Methyl 5-[hydroxy(phenyl)methyl]-3-cyclohexene-1-carboxylate (6n). This
compound was prepared according to the above general procedure from 1g and 2a,
except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml
DMSO/MeOH mixture. The diastereoselectivity of 6n is assigned on the basis of 1H-
NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR
(CDCl3): 7.32 (m, 5H), 5.79 (m, 1H), 5.30 (m, 1H), 4.56 (d, 7.1 Hz, 1H), 3.68 (s, 3H),
2.76 (dtd, 3.7 Hz, 7.1 Hz, 10.2 Hz, 1H), 2.57, (m, 1H), 2.26 (m, 2H), 2.14 (dt, 3.7 Hz,
13.5 Hz, 1H), 2.02 (bs, 1H), 1.81 (ddd, 6.0 Hz, 10.2 Hz, 13.5 Hz, 1H). 13C NMR
(CDCl3): 176.4, 143.0, 128.7, 128.3, 128.0, 127.7, 126.8, 77.0, 52.0, 41.3, 36.5, 27.6,
26.1. HRMS (ESI): calc for [C15H18O3 - OH]+: m/z, 229.1223, found: 229.1223.
Methyl 5-[(4-bromophenyl)(hydroxy)methyl]-3-cyclohexene-1-carboxylate
(6o). This compound was prepared according to the above general procedure from 1g
and 2b, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml
DMSO/MeOH mixture. The diastereoselectivity of 6o is assigned on the basis of 1H-
NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR
(CDCl3): 7.47 (d, 8.4 Hz, 2H), 7.21 (d, 8.4 Hz, 2H), 5.80 (m, 1H), 5.30 (m, 1H), 4.54
(d, 7.2 Hz, 1H), 3.66 (s, 3H), 2.73 (dtd, 3.8 Hz, 7.0 Hz, 10.2 Hz, 1H), 2.52 (m, 1H),
2.26 (m, 2H), 2.13 (bs, 1H), 2.06 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.76 (ddd, 6.1 Hz, 10.2
Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 176.3, 141.9, 131.7, 128.8, 128.5, 127.3, 121.7,
76.2, 52.1, 41.3, 36.5, 27.5, 25.8. HRMS (ESI): calc for [C15H17BrO3 - OH]+: m/z,
307.0328, found: 307.0323.
Methyl 5-[(4-cyanophenyl)(hydroxy)methyl]-3-cyclohexene-1-carboxylate (6p).
This compound was prepared according to the above general procedure from 1g and
2c, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml
DMSO/MeOH mixture. The diastereoselectivity of 6p is assigned on the basis of 1H-
NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR
(CDCl3): 7.63 (d, 8.2 Hz, 2H), 7.46 (d, 8.2 Hz, 2H), 5.86 (m, 1H), 5.34 (m, 1H), 4.68
7
(dd, 2.5 Hz, 6.5 Hz, 1H), 3.66 (s, 3H), 2.75 (dtd, 3.8 Hz, 6.8 Hz, 9.8 Hz, 1H), 2.56 (m,
1H), 2.27 (m, 2H), 2.23 (d, 2.5 Hz, 1H), 1.99 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.72 (ddd, 6.0
Hz, 9.8 Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 176.1, 148.2, 132.5, 129.6, 127.5,
126.9, 119.1, 111.6, 76.1, 52.1, 41.2, 36.5, 27.5, 25.4. HRMS (ESI): calc for
[C16H17NO3+H]+: m/z, 272.1281, found: 272.1286.
Methyl 5-[hydroxy(4-nitrophenyl)methyl]-3-cyclohexene-1-carboxylate (6q).
This compound was prepared according to the above general procedure from 1g and
2d, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml
DMSO/MeOH mixture. The diastereoselectivity of 6q is assigned on the basis of 1H-
NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR
(CDCl3): 8.18 (d, 8.2 Hz, 2H), 7.51 (d, 8.2 Hz, 2H), 5.86 (m, 1H), 5.35 (m, 1H), 4.74
(d, 6.5 Hz, 1H), 3.65 (s, 3H), 2.75 (dtd, 3.8 Hz, 7.0 Hz, 10.0 Hz, 1H), 2.58 (m, 1H),
2.43 (bs, 1H), 2.27 (m, 2H), 1.99 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.71 (ddd, 6.2 Hz, 10.0
Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 176.1, 150.3, 147.6, 129.6, 127.5, 126.8, 123.8,
75.9, 52.1, 41.3, 36.5, 27.4, 25.4. HRMS (ESI): calc for [C15H17NO5+H]+: m/z,
292.1179, found: 292.1181.
Methyl 5-[(4-acetylphenyl)(hydroxy)methyl]-3-cyclohexene-1-carboxylate (6r).
This compound was prepared according to the above general procedure from 1g and
2e, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml
DMSO/MeOH mixture. The diastereoselectivity of 6r is assigned on the basis of 1H-
NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR
(CDCl3): 7.93 (d, 8.3 Hz, 2H), 7.43 (d, 8.3 Hz, 2H), 5.83 (m, 1H), 5.33 (m, 1H), 4.66
(d, 6.6 Hz, 1H), 3.66 (s, 3H), 2.76 (dtd, 3.8 Hz, 6.8 Hz, 10.0 Hz, 1H), 2.59 (s, 3H),
2.59 (m, 1H), 2.27 (m, 3H), 2.05 (dt, 3.8 Hz, 13.5 Hz, 1H), 1.75 (ddd, 6.1 Hz, 10.0
Hz, 13.5 Hz, 1H). 13C NMR (CDCl3): 198.2, 176.2, 148.3, 136.7, 129.0, 128.7, 127.2,
126.9, 76.4, 52.1, 41.3, 36.5, 27.5, 26.9, 25.7. HRMS (ESI): calc for [C17H20O4+H]+:
m/z, 289.1434, found: 289.1430.
Methyl 5-(1-hydroxyhexyl)-3-cyclohexene-1-carboxylate (6s). This compound
was prepared according to the above general procedure from 1g and 2f, except that
0.20 mmol of aldehyde 2f and 0.30 mmol of tetrahydroxydiboron were used in a
0.2/0.2 ml DMSO/MeOH mixture. The diastereoselectivity of 6s is assigned on the
8
basis of 1H-NMR data given in the literature[9,12] for analog stereo defined
compounds. 1H NMR (CDCl3): 5.85 (m, 1H), 5.60 (m, 1H), 3.68 (s, 3H), 3.56 (dt, 5.1
Hz, 6.7 Hz, 1H), 2.79 (dtd, 3.7 Hz, 6.1 Hz, 9.3 Hz, 1H), 2.26 (m, 3H), 2.02 (dt, 3.7
Hz, 13.5 Hz, 1H), 1.82 (ddd, 6.0 Hz, 9.3 Hz, 13.5 Hz, 1H), 1.41 (m, 9H), 0.89 (t, 6.6
Hz). 13C NMR (CDCl3): 176.4, 128.4, 128.4, 74.3, 52.0, 39.5, 36.8, 34.5, 32.2, 27.5,
25.9, 25.1, 23.0, 14.4. HRMS (ESI): calc for [C14H24O3+H]+: m/z, 241.1798, found:
241.1800.
Methyl 5-[hydroxy(3-nitrophenyl)methyl]-3-cyclohexene-1-carboxylate (6t).
This compound was prepared according to the above general procedure from 1g and
2g, except that 0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml
DMSO/MeOH mixture. The diastereoselectivity of 6t is assigned on the basis of 1H-
NMR data given in the literature[9,12] for analog stereo defined compounds. 1H NMR
(CDCl3): 8.21 (s, 1H), 8.13 (d, 8.0 Hz, 1H), 7.68 (d, 8.0 Hz, 1H), 7.52 (t, 8.0 Hz, 1H),
5.87 (m, 1H), 5.34 (m, 1H), 4.74 (dd, 6.6 Hz, 2.9 Hz, 1H), 3.66 (s, 3H), 2.76 (dtd, 3.8
Hz, 6.7 Hz, 9.7 Hz, 1H), 2.60 (m, 1H), 2.34 (d, 2.9 Hz, 1H), 2.28 (m, 2H), 2.02 (dt,
3.8 Hz, 13.5 Hz, 1H), 1.75 (ddd, 6.0 Hz, 9.7 Hz, 13.5 Hz, 1H). 13C NMR (CDCl3):
176.1, 148.6, 145.0, 132.9, 129.6, 129.6, 126.8, 122.9, 121.8, 75.8, 52.1, 41.3, 36.5,
27.5, 25.5. HRMS (ESI): calc for [C15H17NO5+H]+: m/z, 292.1179, found: 292.1171.
Methyl 5-[1-hydroxymethyl]-3-cyclohexene-1-carboxylate (6u). This compound
was prepared according to the above general procedure from 1g and 2h, except that
0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml DMSO/MeOH mixture.
The diastereoselectivity of 6u is assigned on the basis of 1H-NMR data given in the
literature[9,12] for analog stereo defined compounds. 1H NMR (CDCl3): 5.82 (m, 1H),
5.62 (m, 1H), 3.68 (s, 3H), 3.56 (m, 2H), 2.71 (dtd, 4.3 Hz, 7.0 Hz, 9.9 Hz, 1H), 2.40
(m, 1H), 2.27 (m, 2H), 1.92 (m, 2H), 1.63 (bs, 1H), 13C NMR (CDCl3): 176.4, 128.1,
127.3, 66.3, 52.1, 36.8, 36.5, 27.6, 27.3. HRMS (ESI): calc for [C9H14O3 + H]+: m/z,
171.1016, found: 171.1017.
Methyl 5-[1-hydroxyethyl]-3-cyclohexene-1-carboxylate (6v). This compound
was prepared according to the above general procedure from 1g and 2i, except that
0.30 mmol of tetrahydroxydiboron was used in a 0.2/0.2 ml DMSO/MeOH mixture.
The diastereoselectivity of 6u is assigned on the basis of 1H-NMR data given in the
9
literature[9,12] for analog stereo defined compounds. 1H NMR (CDCl3): 5.82 (m, 1H),
5.60 (m, 1H), 3.72 (p, 6.2 Hz, 1H), 3.67 (s, 3H), 2.75 (dtd, 3.9 Hz, 6.8 Hz, 9.7 Hz,
1H), 2.26 (m, 2H), 2.16 (m, 1H), 2.02 (dt, 3.9 Hz, 13.5 Hz, 1H), 1.90 (bs, 1H), 1.83
(ddd, 6.0 Hz, 9.7 Hz, 13.5 Hz, 1H), 1.22 (d, 6.2 Hz, 3H). 13C NMR (CDCl3): 176.4,
128.2, 128.0, 70.3, 52.0, 41.2, 36.7, 27.5, 25.5, 21.0. HRMS (ESI): calc for [C10H16O3
+ H]+: m/z, 185.1172, found: 185.1170.
10
OH
Ph 6a
11
OH
Ph 6a
12
OH
PhBr
6b
13
OH
PhBr
6b
14
OH
PhC
N6c
15
OH
PhC
N6c
16
OH
PhN
O2
6d
17
OH
PhN
O2
6d
18
OH
PhO
6e
19
OH
PhO
6e
20
OH
Ph6f
21
OH
Ph6f
22
OH
C5H
11 6g
23
OH
C5H
11 6g
24
OH
C5H
11
6h
25
OH
C5H
11
6h
26
OH
BnO
6i
27
OH
BnO
6i
28
OH
6j
29
OH
6j
30
OH
CO
OEt
6k
31
OH
CO
OEt
6k
32
OO
6l
33
OO
6l
34
OH
H 6m
35
OH
H 6m
36
OH
CO
OM
e
6nH
37
OH
CO
OM
e
6nH
38
OH
CO
OM
eBr
6o
H
39
OH
CO
OM
eBr
6o
H
40
OH
CO
OM
eC
N
6p
H
41
OH
CO
OM
eC
N
6p
H
42
OH
CO
OM
eN
O2
6q
H
43
OH
CO
OM
eN
O2
6q
H
44
OH
CO
OM
e 6r
O
H
45
OH
CO
OM
e 6r
O
H
46
OH
CO
OM
e 6s
H
47
OH
CO
OM
e 6s
H
48
6tOH
CO
OM
e
NO
2H
49
6tOH
CO
OM
e
NO
2H
50
HO
CO
OM
e
6u
51
HO
CO
OM
e
6u
52
OH
CO
OM
e
H 6v
53
OH
CO
OM
e
H 6v
54
References
[1] Q. Yao, E. P. Kinney, C. Zheng, Org. Lett. 2004, 6, 2997.
[2] J. A. Marshall, S. Xie, J. Org. Chem. 1995, 60, 7230.
[3] (a) J. P. Takahara, Y. Masuyama, Y. Kurusu, J. Am. Chem. Soc. 1992, 114,
2577. (b) D. Basavaiah, P. D. Rao, Tetrahedron: Asymmetry 1995, 6, 789.
[4] O. A. Wallner, K. J. Szabó, Chem. Eur. J. 2003, 9, 4025.
[5] J. M. Coxon, S. J. van Eyk, P. J. Steel, Tetrahedron, 1989, 45, 1029.
[6] O. A. Wallner, K. J. Szabó, J. Org. Chem. 2003, 68, 2934.
[7] K. Fujita, H. Yorimitsu, H. Shinokubo, S. Matsubara, K. Oshima, J. Am.
Chem. Soc. 2001, 123, 12115.
[8] M. Bandini, P. G. Cozzi, S. Licciulli, A. Umani-Ronchi, Synthesis 2004,
409.
[9] S. Kobayashi, K. Nishio, J. Org. Chem. 1994, 59, 6620.
[10] H. Nagano, S. Toi, M. Matsuda, T. Hirasawa, S. Hirasawa, T. Yajima, J.
Chem. Soc. Perkin Trans.2, 2002, 22, 2525.
[11] P. K. Choudhury, F. Foubelo, M. Yus, Tetrahedron, 1999, 55, 10779.
[12] V. J. Olsson, S. Sebelius, N. Selander, K. J. Szabó, J. Am. Chem. Soc., 2006,
128, 4588.