(td, J ) 13.9, 2.7 Hz, 1H), 0.97 (d, J ) 6.6 Hz, 3H) 13C NMR
(100 MHz, pyridine-d5): δ 67.3, 66.2, 46.3, 43.8, 42.3, 26.4, 23.0.
meso-anti-2d:1H NMR (300 MHz, pyridine-d5): δ 4.30 (m, 2H),
2.50 (m, 1H), 2.15 (dm, J ) 13.5 Hz, 1H), 1.99 (dm, J ) 13.2 Hz,
2H), 1.85 (dt, J ) 13.5, 3.0 Hz, 1H), 1.37 (td, J ) 10.2, 2.8 Hz,
2H), 0.94 (d, J ) 6.9 Hz, 3H) 13C NMR (100 MHz, pyridine-d5):
δ 67.4, 42.4, 40.3, 22.7, 22.2
D,L mixture of a diol can be converted into one stereoisomer of
the diol diacetate.1
Experimental Section
General Procedure for the Preparation of 1,3-Cycloal-
kanediols: 1,3-Cyclohexanediol (2b). A Pyrex tube (5 mL) was
charged with 1,3-cyclohexanedione 1b (112 mg, 1 mmol), ruthe-
nium catalyst 3 (11 mg, 0.01 mmol), 2-propanol (1.83 mL, 24
mmol), and toluene (2.5 mL) and fitted with a silicone/Teflon
septum. The septum was closed, and the reaction vessel was inserted
to a microwave oven and heated at 110 °C for 30 min. The solvents
were evaporated, and the crude product was purified by chroma-
tography (CH2Cl2 to remove the yellow band, then EtOAc) to afford
2b (103 mg, 88%) as a colorless oil in a cis/trans ratio of 58:42.
Analytical data were in accordance with those reported in the
literature.1
meso-syn-2d: 1H NMR (300 MHz, pyridine-d5): δ 3.86 (tt, J )
11.0, 4.1 Hz, 2H), 2.83 (dm, J ) 11.6 Hz, 1H), 2.17 (dm, J ) 11.6
Hz, 2H), 1.79 (app. q, J ) 11.2 Hz, 1H), 1.49 (m, 1H), 1.22 (app.
q, J ) 11.6 Hz, 2H), 0.95 (d, J ) 6.6 Hz, 3H) 13C NMR (100
MHz, pyridine-d5): δ 68.6, 46.9, 45.3, 28.7, 22.6
1,3-Cycloheptanediol (2e) via Combined Transfer Hydroge-
nation and Hydrogenation. A Pyrex tube (5 mL) was charged
with 1,3-cycloheptanedione 1e (126 mg, 1 mmol), ruthenium
catalyst 3 (21.7 mg, 0.02 mmol), 2-propanol (1.83 mL, 24 mmol),
and toluene (2.5 mL) and fitted with a silicone/Teflon septum. The
septum was closed, and the atmosphere was exchanged to hydrogen
gas. A balloon filled with hydrogen gas was fitted to the flask, and
the mixture was heated at 80 °C in an oil bath for 24 h. The solvents
were evaporated, and the crude product was purified by chroma-
tography (CH2Cl2 to remove the yellow band, then pentane/EtOAc
1:1) to afford 2h (95 mg, 73%) as a brown oil in a cis/trans ratio
of 48:52. Analytical data for trans-2e were in accordance with those
reported in the literature.26
cis-2e.27 1H NMR (400 MHz, CDCl3): δ 3.87 (app. sep, J )
3.6 Hz, 2H), 2.10 (dt, J ) 13.7, 3.3 Hz, 1H), (2.00-1.81, m, 5H),
(1.76-1.61, m, 4H), (1.55-1.39, m, 2H) 13C NMR (100 MHz,
CDCl3): δ 69.4, 45.4, 37.5, 23.1
1,3-Cyclopentanediol (2f). Following the same procedure as for
2e, the reaction mixture was heated at 80 °C in an oil bath for 48
h. Purification by chromatography (CH2Cl2 to remove the yellow
band, then CH2Cl2/MeOH 9:1) afforded 2f (70 mg, 69%) as a brown
oil in a cis/trans ratio of 69:31. Analytical data were in accordance
with those reported in the literature.28,29
2-Methyl-1,3-cyclohexanediol (2a). Following the general pro-
cedure, the reaction mixture was heated for 60 min in a microwave
oven. Chromatography (CH2Cl2 to remove the yellow band, then
n-pentane/EtOAc 3:2 to 1:2) afforded 2a (111 mg, 85%) as a pale
brown oil in a disatereomeric ratio of 28:36:36. Analytical data
were in accordance with those reported in the literature.3
2,2-Dimethyl-1,3-cyclohexanediol (2c).24 Following the general
procedure, the reaction mixture was heated for 60 min in a
microwave oven. Chromatography (CH2Cl2 to remove the yellow
band, then n-pentane/EtOAc 2:1 to 1:1) afforded 2c (120 mg, 83%)
as a white solid in a cis/trans ratio of 56:44. cis- 2c1H NMR (400
MHz, CDCl3): δ 3.40 (dd, J ) 3.5, 7.9 Hz, 2H), 1.79 (m, 3H),
1.55 (m, 2H), 1.34 (m, 1H), 1.03 (s, 3H), 1.00 (s, 3H) 13C NMR
1
(100 MHz, CDCl3): δ 76.2, 39.7, 29.3, 24.6, 17.1; trans-2c H
NMR (400 MHz, CDCl3): δ 3.67 (dd, J ) 3.3, 7.1 Hz, 2H), 1.72
(m, 2H), 1.64 (m,2H), 1.50 (m, 2H), 0.99 (s, 6H) 13C NMR (100
MHz, CDCl3): δ 74.9, 39.8, 29.4, 21.1, 19.1
5-Methyl-1,3-cyclohexanediol (2d).2 Following the general
procedure, the reaction mixture was heated at 120 °C for 2 h in a
microwave oven. Purification by distillation (230 °C, 0.6 mbar)
afforded 2d (95.5 mg, 73%) as a white solid in a diasteromeric
ratio of D,L-2d (trans-2d)/meso-anti-2d/meso-syn-2d (all-cis-2d) of
35:19:46.25 D,L-2d 1H NMR (400 MHz, pyridine-d5): δ 4.67 (tt, J
) 15.4, 4.2 Hz, 1H), 4.51 (m, 1H), 2.63 (dm, J ) 12.8 Hz, 1H),
2.33 (dm, J ) 11.3 Hz, 2H), 1.98 (dm, J ) 13.4 Hz, 1H), 1.71 (td,
J ) 11.3, 2.7 Hz, 1H), 1.30 (app. q, J ) 12.8 Hz, 1H), 1.18
1,3-Indanediol (2g). Following the same procedure as stated
previously, the reaction mixture was heated at 80 °C in an oil bath
for 30 h. Purification by distillation (300 °C, 0.6 mbar) afforded
2g (140 mg, 93%) as a white solid in a cis/trans ratio of 91:9.
Analytical data were in accordance with those reported in the
literature.30
Acknowledgment. Financial support from the Swedish
Foundation for Strategic Research and the Swedish Research
Council is gratefully acknowledged.
(20) The corresponding hydrogenation using Pd/C gave 2-methyl-2-
cyclohexen-1-ol as the major product.
(21) Lutsenko, S.; Moberg, C. Tetrahedron: Asymmetry 2001, 12, 2529-
2532.
(22) Paetzold, J.; Ba¨ckvall, J. E. J. Am. Chem. Soc. 2005, 127, 17620-
17621.
(23) There seemed to be a loss of H2 (g) from the catalyst over time, so
a constant atmosphere of hydrogen was needed. Since 2-propanol has a
boiling point of 82 °C, the temperature had to be decreased. For H2
elimination from 3a, see Casey, C. P.; Johnson, J. B.; Singer, S. W.; Cui,
Q. J. Am. Chem. Soc. 2005, 127, 3100-3109.
(24) Jacobson, B. M.; Soteropoulos, P.; Bahadori, S. J. Org. Chem. 1988,
53, 3247-3255.
(25) The three isomers of 2d are
Supporting Information Available: General experimental
1
procedures, characterization data, and copies of H NMR and 13C
NMR spectra of compounds 2c, 2d, and 2e. This material is
JO0612527
(26) Kaku, H.; Tanaka, M.; Norimine, Y.; Miyashita, Y.; Suemune, K.;
Sakai, K. Tetrahedron: Asymmetry 1997, 2, 195-202.
(27) Adam, W.; Balci, M. J. Am. Chem. Soc. 1979, 101, 7537-7541.
(28) Dermatakis, A.; Luk, K. C.; DePinto, W. Bioorg. Med. Chem. 2003,
11, 1873-1881.
(29) Chen, Z.; Halterman, R. L. Organometallics 1994, 13, 3932-3942.
(30) Clerici, A.; Pastori, N.; Porta, O. Eur. J. Org. Chem. 2002, 19,
3326-3335.
here called D,L-2d, meso-syn-2d (all-cis-2d), and meso-anti-2d, respectively.
J. Org. Chem, Vol. 71, No. 22, 2006 8625