D. Shklyaruck, E. Matiushenkov / Tetrahedron: Asymmetry 22 (2011) 1448–1454
1453
chromatography (petroleum ether/ethyl acetate) to give imide 16
(1.76 g, 93%) as a colourless viscous oil; [
Acknowledgments
a]
D = ꢀ6.9 (c 2.70, CHCl3);
1H NMR (CDCl3) d 0.78 (d, J = 6.9, Hz, 3H, 6-Me), 0.95 (d, J = 6.9 Hz,
3H, 60-Me), 0.95 (s, 3H, Me in bornane), 1.13 (s, 3H, Me0 in bor-
nane), 1.18 (d, J = 6.5, Hz, 3H, 2-Me), 1.30–1.42 (m, 2H, CHCHHCHH
in bornane), 1.70–1.79 (m, 1H, 6-H), 1.81–1.92 (m, 3H, CHCHHCHH
in bornane), 2.02–2.06 (m, 2H, CHCHHCH in bornane), 2.18 (dd,
J = 13.8, 5.1 Hz, 1H, 3-H), 2.29 (d, J = 2.9 Hz, 1H, OH), 2.41 (dd,
J = 13.8, 9.8 Hz, 1H, 30-H), 3.33–3.42 (m, 1H, 2-H), 3.42 (d,
J = 13.8 Hz, 1H, CHHS in bornane), 3.49 (d, J = 13.8 Hz, 1H, CHHS
in bornane), 3.71 (dd, J = 7.2, 2.9 Hz, 1H, 5-H), 3.88 (dd, J = 6.4,
6.1 Hz, 1H, CHN in bornane), 4.88–4.92 (m, 2H, C@CH2); 13C NMR
(CDCl3) d 17.6, 18.1, 19.5, 19.9, 20.8, 26.3, 31.4, 33.0, 37.0, 38.5,
39.6, 44.7, 47.4, 48.2, 53.2, 65.6, 81.5, 113.7, 147.8, 176.0; IR
This work was carried out with the support of the Ministry of
Education of the Republic of Belarus. We thank Mr. Aleksei Raiman
for assistance in editing the English version of the manuscript.
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A solution of 16 (1.35 g, 3.52 mmol) and freshly prepared
Wilkinson’s catalyst14 (Ph3P)3RhCl (0.81 g, 0.88 mmol) in dry ben-
zene (70 mL) was stirred under a hydrogen atmosphere (1 bar) at rt
for 7 h. The solution was concentrated under reduced pressure, and
the residue was purified by flash column chromatography (petro-
leum ether/ethyl acetate) to give 17 (1.28 g, 94%) as a pale yellow
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ourless viscous oil (240 mg); [
a]
D = ꢀ8.8 (c 2.22, CHCl3); 1H NMR
(CDCl3) d 0.82 (d, J = 6.8, Hz, 3H, 6-Me), 0.86 (d, J = 6.4, Hz, 3H, 4-
Me), 0.95 (d, J = 6.9, Hz, 3H, 60-Me), 0.96 (s, 3H, Me in bornane),
1.15 (s, 3H, Me0 in bornane), 1.16 (d, J = 6.5, Hz, 3H, 2-Me), 1.30–
1.43 (m, 3H, CHCHHCHH in bornane, OH), 1.49–1.55 (m, 1H, 3-
H), 1.62–1.73 (m, 3H, 30-H, 4-H, 6-H), 1.81–1.92 (m, 3H,
CHCHHCHH in bornane), 2.01–2.09 (m, 2H, CHCHHCH in bornane),
3.11–3.19 (m, 2H, 2-H, 5-H), 3.43 (d, J = 13.8 Hz, 1H, CHHS in bor-
nane), 3.49 (d, J = 13.8 Hz, 1H, CHHS in bornane), 3.88 (dd, J = 6.4,
6.4 Hz, 1H, CHN in bornane); 13C NMR (CDCl3) d 12.7, 17.0, 18.7,
19.1, 19.8, 21.1, 26.4, 31.2, 32.7, 32.9, 37.6, 38.7, 39.3, 44.7, 47.7,
11. (a) Kozyrkov, Y. Y.; Kulinkovich, O. G. Synlett 2002, 443–446; (b) Kulinkovich,
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48.2, 53.2, 65.4, 79.3, 176.7; IR (CCl4) m
max: 3569, 1698 cmꢀ1. Anal.
Calcd for C20H35NO4S: C, 62.30; H, 9.15. Found: C, 62.23; H, 9.25.
4.13. (3S,5S,6S)-Tetrahydro-6-isopropyl-3,5-dimethylpyran-2-
one 3
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A solution of freshly prepared Wilkinson’s catalyst (208 mg,
0.22 mmol) in dry benzene (4 mL) was degassed and then stirred
under a hydrogen atmosphere (1 bar) at rt for 30 min. A solution
of the unsaturated lactone 4 (252 mg, 1.50 mmol) in benzene
(2 mL) was added, and the mixture was stirred under a hydrogen
atmosphere (1 bar) at rt for 3 h. The solution was concentrated un-
der reduced pressure, and the residue was purified by flash column
chromatography (petroleum ether/ethyl acetate) to give the target
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and ester fragments, see: Hurski, A. L. Ph.D. Thesis, Belarusian State University,
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lactone 3 (250 mg, 98%) as a colourless liquid; [
a
]
D = ꢀ11.4 (c 2.18,
CHCl3); 1H NMR (CDCl3) d 0.87 (d, J = 6.5 Hz, 3H, 7-Me), 0.98 (d,
J = 7.2 Hz, 3H, 5-Me), 1.07 (d, J = 6.5 Hz, 3H, 70-Me), 1.29 (d,
J = 7.2 Hz, 3H, 3-Me), 1.66 (ddd, J = 13.4, 12.5, 3.8 Hz, 1H, 4-Hax),
1.81 (d of sept., J = 10.0, 6.5 Hz, 1H, 7-H), 1.91 (ddd, J = 13.4, 6.5,
3.1 Hz, 1H, 4-Heq), 2.14 (m, 2.09–2.17, 1H, 5-H), 2.60 (ddd,
J = 12.5, 7.2, 6.5 Hz, 1H, 3-H), 3.82 (dd, J = 10.0, 2.6 Hz, 1H, 6-H);
13C NMR (CDCl3) d 10.5, 17.8, 17.9, 19.7, 27.8, 30.1, 31.1, 36.4,
19. Haas, M. J. Ph.D. Thesis, Rheinisch-Westfälischen Technischen Hochschule
Aachen, 2005.
20. We thank Professor Dr. Hiromasa Kiyota (Tohoku University, Graduate School
of Agricultural Sciences, Division of Life Science, Laboratory of Applied
Bioorganic Chemistry) for the original 1H NMR spectrum of lactone 1.
21. For examples of diastereoselective homogeneous hydrogenation of allylic
alcohols see: (a) Evans, D. A.; Morrissey, M. M. J. Am. Chem. Soc. 1984, 106,
3866–3868; (b) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93,
1307–1370; (c) Nakata, M.; Hiroyuki, E.; Kinoshita, M. Bull. Chem. Soc. Jpn.
89.4, 174.5; IR (CCl4)
(M+, 1.4), 127 (41.4), 56 (100.0), 43 (96.0). Anal. Calcd for
10H18O2: C, 70.55; H, 10.66. Found: C, 70.53; H, 10.71.
m
max: 1738 cmꢀ1; MS (EI): m/z (%) = 170
C